EP1759399A2 - Heterodiamondoid-containing field emission devices - Google Patents

Heterodiamondoid-containing field emission devices

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Publication number
EP1759399A2
EP1759399A2 EP05722588A EP05722588A EP1759399A2 EP 1759399 A2 EP1759399 A2 EP 1759399A2 EP 05722588 A EP05722588 A EP 05722588A EP 05722588 A EP05722588 A EP 05722588A EP 1759399 A2 EP1759399 A2 EP 1759399A2
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EP
European Patent Office
Prior art keywords
heterodiamondoid
diamond
field emission
emission device
cathode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05722588A
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German (de)
French (fr)
Inventor
Jeremy E. Dahl
Robert M. Carlson
Shenggao Liu
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Chevron USA Inc
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Chevron USA Inc
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Publication date
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Publication of EP1759399A2 publication Critical patent/EP1759399A2/en
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H01J1/30—Cold cathodes, e.g. field-emissive cathode
    • H01J1/304—Field-emissive cathodes
    • H01J1/3048—Distributed particle emitters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
    • H01J1/02—Main electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2201/00—Electrodes common to discharge tubes
    • H01J2201/30—Cold cathodes
    • H01J2201/304—Field emission cathodes
    • H01J2201/30446—Field emission cathodes characterised by the emitter material
    • H01J2201/30453—Carbon types
    • H01J2201/30457—Diamond

Definitions

  • Embodiments of the present invention are generally directed toward novel uses of heterodiamondoids and heterodiamondoid-containing materials in field emission devices.
  • the heteroatoms of the heterodiamondoids of the present embodiments are electron donating species
  • the field emission device (FED) contains an electron-emitting cold cathode.
  • Carbon-containing materials offer a variety of potential uses in microelectronics. As an element, carbon displays a variety of different structures, some crystalline, some amorphous, and some having regions of both, but each form having a distinct and potentially useful set of properties.
  • a review of carbon's structure-property relationships has been presented by S. Prawer in a chapter titled "The Wonderful World of Carbon," in Physics of Novel Materials (World Scientific, Singapore, 1999), pp. 205-234. Prawer suggests the two most important parameters that may be used to predict the properties of a carbon-containing material are, first, the ratio of sp 2 to sp 3 bonding in a material, and second, microstructure, including the crystallite size of the material, i.e. the size of its individual grains. Elemental carbon has the electronic structure ls 2 2s 2 2p 2 , where the outer shell
  • the so-called sp 3 hybridization comprises four identical ⁇ bonds arranged in a tetrahedral manner.
  • the so-called sp -hybridization comprises three trigonal (as well as planar) ⁇ bonds with an unhybridized p electron occupying a ⁇ orbital in a bond oriented perpendicular to the plane of the ⁇ bonds.
  • At the "extremes" of crystalline morphology are diamond and graphite. In diamond, the carbon atoms are tetrahedrally bonded with sp 3 -hybridization.
  • Graphite comprises planar "sheets" of sp 2 -hybridized atoms, where the sheets interact weakly through perpendicularly oriented ⁇ bonds. Carbon exists in other morphologies as well, including amorphous forms called “diamond-like carbon," and the highly symmetrical spherical and rod- shaped structures called “fullerenes” and “nanotubes,” respectively. Diamond is an exceptional material because it scores highest (or lowest, depending on one's point of view) in a number of different categories of properties. Not only is it the hardest material known, but it has the highest thermal conductivity of any material at room temperature.
  • Unhybridized p electrons associated with sp 2 -hybridization form ⁇ bonds in these materials, where the ⁇ bonded electrons are predominantly delocalized. This gives rise to the enhanced electrical conductivity of materials with sp bonding, such as graphite.
  • sp -hybridization results in the extremely hard, electrically insulating and transparent characteristics of diamond.
  • the hydrogen content of a diamond-like material will be directly related to the type of bonding it has. In diamond-like materials the bandgap gets larger as the hydrogen content increases, and hardness often decreases.
  • the loss of hydrogen from a diamond-like carbon film results in an increase in electrical activity and the loss of other diamond-like properties as well.
  • diamond-like carbon may be used to describe two different classes of amorphous carbon films, one denoted as “a:C-H,” because hydrogen acts to terminate dangling bonds on the surface of the film, and a second hydrogen-free version given the name "ta-C” because a majority of the carbon atoms are tetrahedrally coordinated with sp 3 - hybridization.
  • the remaining carbons of ta-C are surface atoms that are substantially sp 2 -hybridized.
  • a:C-H dangling bonds can relax to the sp 2 (graphitic) configuration.
  • tetrahedral amorphous carbon ta-C
  • ta-C tetrahedral amorphous carbon
  • the maximum sp 3 content of a ta-C film is about 80 to 90 percent.
  • ta-C Those carbon atoms that are sp 2 bonded tend to group into small clusters that prevent the formation of dangling bonds.
  • the properties of ta-C depend primarily on the fraction of atoms having the sp 3 , or diamond-like configuration. Unlike CND diamond, there is no hydrogen in ta-C to passivate the surface and to prevent graphite-like structures from forming. The fact that graphite regions do not appear to form is attributed to the existence of isolated sp bonding pairs and to compressive stresses that build up within the bulk of the material.
  • the microstructure of a diamond and/or diamond-like material further determines its properties, to some degree because the microstructure influences the type of bonding content.
  • Nanocrystalline diamond films have grain sizes in the three to five nanometer range, and it has been reported that nearly 10 percent of the carbon atoms in a nanocrystalline diamond film reside in grain boundaries.
  • nanocrystalline diamond grain boundary is reported to be a high-energy, high angle twist grain boundary, where the carbon atoms are largely ⁇ -bonded. There may also be sp 2 bonded dimers, and chain segments with sp 3 -hybridized dangling bonds. Nanocrystalline diamond is apparently electrically conductive, and it appears that the grain boundaries are responsible for the electrical conductivity. The author states that a nanocrystalline material is essentially a new type of diamond film whose properties are largely determined by the bonding of the carbons within grain boundaries. Another allotrope of carbon known as the fullerenes (and their counterparts carbon nanotubes) has been discussed by M.S. Dresslehaus et al.
  • Fullerenes have an even number of carbon atoms arranged in the form of a closed hollow cage, wherein carbon-carbon bonds on the surface of the cage define a polyhedral structure.
  • the fullerene in the greatest abundance is the C 60 molecule, although C 70 and C 80 fullerenes are also possible.
  • Each carbon atom in the C 60 fullerene is trigonally bonded with sp 2 -hybridization to three other carbon atoms.
  • C 60 fullerene is described by Dresslehaus as a "rolled up" graphine sheet forming a closed shell (where the term “graphine” means a single layer of crystalline graphite).
  • Twenty of the 32 faces on the regular truncated icosahedron are hexagons, with the remaining 12 being pentagons. Every carbon atom in the C 60 fullerene sits on an equivalent lattice site, although the three bonds emanating from each atom are not equivalent. The four valence electrons of each carbon atom are involved in covalent bonding, so that two of the three bonds on the pentagon perimeter are electron-poor single bonds, and one bond between two hexagons is an electron-rich double bond.
  • a fullerene such as C 60 is further stabilized by the Kekule structure of alternating single and double bonds around the hexagonal face.
  • Dresslehaus et al. further teach that, electronically, the C 60 fullerene molecule has 60 ⁇ electrons, one ⁇ electronic state for each carbon atom. Since the highest occupied molecular orbital is fully occupied and the lowest un-occupied molecular orbital is completely empty, the C 60 fullerene is considered to be a semiconductor with very high resistivity.
  • Fullerene molecules exhibit weak van der Waals cohesive interactive forces toward one another when aggregated as a solid. The following table summarizes a few of the properties of diamond, DLC (both ta-C and a:C-H), graphite, and fullerenes:
  • Diamondoids are bridged-ring cycloalkanes that comprise adamantane, diamantane, triamantane, and the tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers, etc., of adamantane (tricyclo[3.3.1.1 3,7 ] decane), adamantane having the stoichiometric formula C ⁇ 0 H ⁇ 6 , in which various adamantane units are face-fused to form larger structures. These adamantane units are essentially subunits of diamondoids.
  • the compounds have a "diamondoid" topology in that their carbon atom arrangements are superimposable on a fragment of an FCC (face centered cubic) diamond lattice.
  • Diamondoids are highly unusual forms of carbon because while they are hydrocarbons, with molecular sizes ranging in general from about 0.2 to 20 nm (averaged in various directions), they simultaneously display the electronic properties of an ultrananocrystalline diamond. As hydrocarbons they can self- assemble into a van der Waals solid, possibly in a repeating array with each diamondoid assembling in a specific orientation. The solid results from cohesive dispersive forces between adjacent C-H x groups, the forces more commonly seen in normal alkanes.
  • diamond nanocrystallites the carbon atoms are entirely sp 3 -hybridized, but because of the small size of the diamondoids, only a small fraction of the carbon atoms are bonded exclusively to other carbon atoms. The majority have at least one hydrogen nearest neighbor. Thus, the majority of the carbon atoms of a diamondoid occupy surface sites (or near surface sites), giving rise to electronic states that are significantly different energetically from bulk energy states. Accordingly, diamondoids are expected to have unusual electronic properties. To the inventors' knowledge, adamantane, substituted adamantanes, and perhaps diamantane are the only readily available diamondoids.
  • Embodiments of the present invention are generally directed toward novel uses of heterodiamondoids and heterodiamondoid-containing materials in field emission devices.
  • the heteroatoms of the heterodiamondoids of the present embodiments are electron donating species, and the field emission device (FED) contains an electron-emitting cathode.
  • FED field emission device
  • the term "heterodiamondoid” as used herein refers to a diamondoid that contains a heteroatom typically substitutionally positioned on a lattice site of the diamond crystal structure.
  • a heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic.
  • “Substitutionally positioned” means that the heteroatom has replaced a carbon host atom in the diamond lattice.
  • Exemplary methods for fabricating w-type materials from heterodiamondoid compounds include CVD techniques, polymerization techniques, crystallization of the heterodiamondoids by themselves, or crystallization of the heterodiamondoids along with with other materials, and use of diamondoids and/or heterodiamondoids at the molecular level.
  • a heterodiamondoid or heterodiamondoid-containing material is utilized as a cathode filament in a field emission device suitable for use, among other places, in flat panel displays. The unique properties of a heteroatom-containing diamondoid make this possible.
  • the filament material (wherein the term
  • filament is used interchangeably with the term “cathode”
  • filament may be in the form of a film or a fiber.
  • the heterodiamondoid-containing material is selected from the group consisting of a heterodiamondoid-containing polymer, a heterodiamondoid- > containing CND film, and a heterodiamondoid-containing molecular crystal.
  • the electron affinity of the cathode is less than about 3 eN, and the electron affinity may be negative.
  • FIG. 1 is an overview of the embodiments of the present invention, showing the steps of isolating diamondoids from petroleum, synthesizing heterodiamondoids, preparing ⁇ -type materials therefrom, and then fabricating a field emission device (FED) based on the heterodiamondoid-containing material;
  • FIG. 2 shows an exemplary process flow for isolating diamondoids from petroleum;
  • FIG. 3 illustrates the relationship of a diamondoid to the diamond crystal lattice, and enumerates by stoichiometric formula many of the diamondoids available;
  • FIGS. 4A-B illustrate exemplary positions of the electron-donating heteroatom on a carbon atom lattice site of two exemplary diamondoids;
  • FIGS. 5A-B illustrate exemplary pathways for synthetically producing a nitrogen-containing heterodiamondoid;
  • FIG. 6 illustrates an exemplary processing reactor in which an n-type heterodiamondoid material may be made using chemical vapor deposition (CND) techniques;
  • FIGS. 7A-C illustrate an exemplary process whereby a heterodiamondoid may be used to introduce dopant impurity atoms into a growing diamond film;
  • FIG. 8 is an exemplary reaction scheme for the synthesis of a polymer from heterodiamondoids;
  • FIG. 9A- ⁇ show exemplary linking groups that may be electrically conducting, and that may be used to link heterodiamondoids to produce ⁇ -type materials
  • FIG. 10 illustrates an exemplary -type material fabricated from heterodiamondoids linked by polyaniline oligomers
  • FIG. 11 shows how [1(2,3)4] pentamantane packs to form a molecular crystal
  • FIG. 12 shows how individual heterodiamondoids may be coupled to form an n-type heterodiamondoid cluster at the molecular level, where such a cluster may contain j ⁇ -type heterodiamondoids as well
  • FIG. 10 illustrates an exemplary -type material fabricated from heterodiamondoids linked by polyaniline oligomers
  • FIG. 11 shows how [1(2,3)4] pentamantane packs to form a molecular crystal
  • FIG. 12 shows how individual heterodiamondoids may be coupled to form an n-type heterodiamondoid cluster at the mo
  • FIG. 13 is a schematic, cross-sectional diagram of an exemplary field emission device, wherein a single diamondoid, or diamondoid-containing material may be used as the cathode filament component of the device.
  • DETAILED DESCRIPTION OF THE INVENTION The present disclosure will be organized as follows: first, a definition of diamondoids and heterodiamondoids will be given, followed by a description of how diamondoids may be isolated from petroleum feedstocks. Next, exemplary methods for synthesizing electron-donating heterodiamondoids will be given, followed by how 72 -type heterodiamondoid materials may be prepared from the electron-donating heterodiamondoids.
  • n-type diamond will be discussed briefly, and how those properties are contemplated to relate to heterodiamondoid- containing field emission devices.
  • present disclosure will conclude with examples of the actual synthesis of some nitrogen-containing heterodiamondoids.
  • heterodiamondoids refers to substituted and unsubstituted caged compounds of the adamantane series.
  • the “lower diamondoids” are defined to be adamantane, diamantane, and triamantane, including substituted and unsubstituted compounds thereof.
  • “Higher diamondoids” are defined to include tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantane, and the like, including all isomers and stereoisomers thereof.
  • the compounds have a "diamondoid" topology, which means their carbon atom arrangement is superimposable on a fragment of an FCC diamond lattice.
  • Substituted diamondoids comprise from 1 to 10 and preferably 1 to 4 independently- selected alkyl substituents.
  • Adamantane chemistry has been reviewed by Fort, Jr. et al. in "Adamantane: Consequences of the Diamondoid Structure," Chem. Rev. vol. 64, pp. 277-300 (1964).
  • Adamantane is the smallest member of the diamondoid series and may be thought of as a single cage crystalline subunit.
  • Diamantane contains two subunits, triamantane three, tetramantane four, and so on.
  • the number of possible isomers increases non-linearly with each higher member of the diamondoid series, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, etc.
  • Adamantane which is commercially available, has been studied extensively.
  • the four tetramantane structures are isO-tetramantane [1(2)3], anti- tetramantane [121] and two enantiomers of sfew-tetramantane [123], with the bracketed nomenclature for these diamondoids in accordance with a convention established by Balaban et al. in "Systematic Classification and Nomenclature of Diamond Hydrocarbons-I," Tetrahedron vol. 34, pp. 3599-3606 (1978). All four tetramantanes have the formula C 2 H 28 (molecular weight 292).
  • pentamantanes there are ten possible pentamantanes, nine having the molecular formula C 26 H 2 (molecular weight 344) and among these nine, there are three pairs of enantiomers represented generally by [12(1)3], [1234], [1213] with the nine enantiomeric pentamantanes represented by [12(3)4], [1(2,3)4], [1212].
  • pentamantane [1231] represented by the molecular formula C 5 H 3 o (molecular weight 330).
  • heptamantanes 67 have the molecular formula C 33 H 38 (molecular weight 434), six have the molecular formula C 32 H 36 (molecular weight 420) and the remaining two have the molecular formula C 30 H 34 (molecular weight 394).
  • Octamantanes possess eight of the adamantane subunits and exist with five different molecular weights. Among the octamantanes, 18 have the molecular formula C 34 H 38 (molecular weight 446). Octamantanes also have the molecular formula C 38 H 4 (molecular weight 500); C 37 H 42 (molecular weight 486); C 36 H 40 (molecular weight 472), and C 33 H 36 (molecular weight 432).
  • Nonamantanes exist within six families of different molecular weights having the following molecular formulas: C 42 H 48 (molecular weight 552), C 4 ⁇ H 46 (molecular weight 538), C 40 H 44 (molecular weight 524, C 38 H 42 (molecular weight 498), C 37 H 40 (molecular weight 484) and C 34 H 36 (molecular weight 444).
  • Decamantane exists within families of seven different molecular weights.
  • the decamantanes there is a single decamantane having the molecular formula C 35 H 36 (molecular weight 456) which is structurally compact in relation to the other decamantanes.
  • decamantane families have the molecular formulas: C 46 H 52 (molecular weight 604); C 45 H 50 (molecular weight 590); C 44 H 8 (molecular weight 576); C 42 H 46 (molecular weight 550); C 4 ⁇ H 44 (molecular weight 536); and C 38 H 40 (molecular weight 496).
  • Undecamantane exists within families of eight different molecular weights.
  • undecamantanes there are two undecamantanes having the molecular formula C 39 H 40 (molecular weight 508) which are structurally compact in relation to the other undecamantanes.
  • the other undecamantane families have the molecular formulas C 4 ⁇ H 42 (molecular weight 534); C 4 H 44 (molecular weight 548); C 45 H 48 (molecular weight 588); C 46 H 50 (molecular weight 602); C 48 H 5 (molecular weight 628); C 4 H 54 (molecular weight 642); and C5oH 56 (molecular weight 656).
  • heteroatom refers to a diamondoid that contains a heteroatom typically substitutionally positioned on a lattice site of the diamond crystal structure.
  • a heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic.
  • substitutionally positioned means that the heteroatom has replaced a carbon host atom in the diamond lattice. Although most heteroatoms are substitutionally positioned, they may in some cases be found in interstitial sites as well.
  • a heterodiamondoid may be functionalized or derivatized; such compounds may be referred to as substituted heterodiamondoids.
  • an »-type diamondoid typically refers to an r ⁇ -type heterodiamondoid, but in some cases the rc-type material may comprise diamondoids with no heteroatom.
  • heteroadamantane and heterodiamantane compounds have been reported in the literature, to the inventors' knowledge, no hetero triamantane or higher compounds have been previously synthesized, and there is no reported case of the use of a heterodiamondoid, including heteroadamantane or heterodiamantane compounds as «-type materials as part of a field emission device, such as the cathode of the device.
  • FIG. 2 shows a process flow illustrated in schematic form, wherein diamondoids may be extracted from petroleum feedstocks, and FIG. 3 enumerates the various diamondoid isomers that are available according to embodiments of the present invention.
  • Feedstocks that contain recoverable amounts of higher diamondoids include, for example, natural gas condensates and refinery streams resulting from cracking, distillation, coking processes, and the like. Particularly preferred feedstocks originate from the Norphlet Formation in the Gulf of Mexico and the LeDuc Formation in Canada. These feedstocks contain large proportions of lower diamondoids (often as much as about two thirds) and lower but significant amounts of higher diamondoids (often as much as about 0.3 to 0.5 percent by weight).
  • a preferred separation method typically includes distillation of the feedstock. This can remove low-boiling, non-diamondoid components. It can also remove or separate out lower and higher diamondoid components having a boiling point less than that of the higher diamondoid(s) selected for isolation.
  • the lower cuts will be enriched in lower diamondoids and low boiling point non- diamondoid materials.
  • Distillation can be operated to provide several cuts in the temperature range of interest to provide the initial isolation of the identified higher diamondoid.
  • the cuts, which are enriched in higher diamondoids or the diamondoid of interest, are retained and may require further purification.
  • Other methods for the removal of contaminants and further purification of an enriched diamondoid fraction can additionally include the following nonlimiting examples: size separation techniques, evaporation either under normal or reduced pressure, sublimation, crystallization, chromatography, well head separators, flash distillation, fixed and fluid bed reactors, reduced pressure, and the like.
  • the removal of non-diamondoids may also include a thermal treatment step either prior or subsequent to distillation.
  • the thermal treatment step may include a hydrotreating step, a hydrocracking step, a hydroprocessing step, or a pyrolysis step.
  • Thermal treatment is an effective method to remove hydrocarbonaceous, non- diamondoid components from the feedstock, and one embodiment of it, pyrolysis, is effected by heating the feedstock under vacuum conditions, or in an inert atmosphere, to a temperature of at least about 390°C, and most preferably to a temperature in the range of about 410 to 450°C. Pyrolysis is continued for a sufficient length of time, and at a sufficiently high temperature, to thermally degrade at least about 10 percent by weight of the non-diamondoid components that were in the feed material prior to pyrolysis.
  • At least about 50 percent by weight, and even more preferably at least 90 percent by weight of the non- diamondoids are thermally degraded. While pyrolysis is preferred in one embodiment, it is not always necessary to facilitate the recovery, isolation or purification of diamondoids. Other separation methods may allow for the concentration of diamondoids to be sufficiently high given certain feedstocks such that direct purification methods such as chromatography including preparative gas chromatography and high performance liquid chromatography, crystallization, fractional sublimation may be used to isolate diamondoids. Even after distillation or pyroly sis/distillation, further purification of the material may be desired to provide selected diamondoids for use in the compositions employed in this invention.
  • Such purification techniques include chromatography, crystallization, thermal diffusion techniques, zone refining, progressive recrystallization, size separation, and the like.
  • the recovered feedstock is subjected to the following additional procedures: 1) gravity column cliromatography using silver nitrate impregnated silica gel; 2) two-column preparative capillary gas chromatography to isolate diamondoids; and/or 3) crystallization to provide crystals of the highly concentrated diamondoids.
  • An alternative process is to use single or multiple column liquid chromatography, including high performance liquid chromatography, to isolate the diamondoids of interest. As above, multiple columns with different selectivities may be used. Further processing using these methods allow for more refined separations which can lead to a substantially pure component.
  • FIG. 2 shows a process flow illustrated in schematic form, wherein diamondoids may be extracted from petroleum feedstocks
  • FIG. 3 enumerates the various diamondoid isomers that are available from embodiments of the present invention.
  • heterodiamondoids refers to a diamondoid that contains a heteroatom typically substitionally positioned on a lattice site of the diamond crystal structure.
  • a heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic.
  • Substitutionally positioned means that the heteroatom has replaced a carbon host atom in the diamond lattice. Although most heteroatoms are substitutionally positioned, they may in some cases be found in interstitial sites as well.
  • FIG. 4 illustrates exemplary heterodiamondoids, indicating the types of carbon positions where a heteroatom may be substitutionally positioned.
  • the heteroatom may be an electron donating element such as N, P, or As, or a hole donating element such as B or Al.
  • the nitrogen-containing heterodiamondoid since it is the properties of the electron-donating nitrogen atom that are the focus of the present field emission devices. An exemplary synthesis of such heterodiamondoids will be discussed next.
  • heteroadamantane and heterodiamantane compounds have been synthesized in the past, and this may suggest a starting point for the synthesis of heterodiamondoids having more than two or three fused adamantane subunits, it will be appreciated by those skilled in the art that the complexity of the individual reactions and overall synthetic pathways increase as the number of adamantane subunits increases. For example, it may be necessary to employ protecting groups, or it may become more difficult to solubilize the reactants, or the reaction conditions may be vastly different from those that would have been used for the analagous reaction with adamantane.
  • a 2-azaadamantane compound may be synthesized from a bicyclo[3.3.1]nonane-3,7-dione, as reported by J.G. Henkel and W.C. Faith, in "Neighboring group effects in the ⁇ -halo amines. Synthesis and solvolytic reactivity of the ⁇ «tz ' -4-substituted 2-azaadamantyl system," in J Org. Chem. Vol. 46, No. 24, pp. 4953-4959 (1981). The dione may be converted by reductive amination
  • FIG. 5 A An exemplary reaction pathway for synthesizing a nitrogen-containing hetero tso-tetramantane is illustrated in FIG. 5 A. It will be known to those of ordinary skill in the art that the reactions conditions of the pathway depicted in FIG. 5 A will be substantially different from those of Eguchi due to the differences in size, solubility, and reactivities of tetramantane in relation to adamantane. A second pathway available for synthesizing nitrogen containing heterodiamondoids is illustrated in FIG. 5B.
  • a phosphorus-containing heterodiamondoid may be synthesized by adapting the pathway outlined by J. J. Meeu Giveaway et. al in "Synthesis of 1-phosphaadamantane," Tetrahedron Nol. 39, No. 24, pp. 4225-4228 (1983). It is contemplated that such a pathway may be able to synthesize heterodiamondoids that contain both nitrogen and phosphorus atoms substitutionally positioned in the diamondoid structure, with the advantages of having two different types of electron-donating heteroatoms in the same structure.
  • the resulting heterodiamondoid may be functionalized to generate an electron-donating material according to embodiments of the present invention.
  • the diamondoid (having no impurity atoms) may be functionalized first, and then converted to the heteroatom form. Further information on the synthesis of heterodiamondoids is provided in a
  • FIG. 1 An overview of exemplary methods for fabricating n-type materials from heterodiamondoid molecules was shown in FIG. 1. These methods included CND techniques, polymerization techniques, crystallization of the heterodiamondoids by themselves, or crystallization of the heterodiamondoids along with with other materials, and use of diamondoids and/or heterodiamondoids at the molecular level.
  • material preparation refers to processes that take the heterodiamondoids after they have been synthesized from diamondoid feedstocks, and fabricates them into ⁇ -type diamondoid-containing materials.
  • heterodiamondoids are injected into a reactor carrying out a conventional CND process such that the heterodiamondoids are added to and become a part of an extended diamond structure, and the heteroatom, being substitutionally positioned on a diamond lattice site, behaves like a dopant in conventionally produced doped diamond.
  • the heterodiamondoids may be derivatized (or functionalized) with functional groups capable of undergoing a polymerization reaction, and in one variation, the functional groups linking two adjacent heterodiamondoids are electrically semiconducting.
  • the n-type material comprises only heterodiamondoids in a bulk heterodiamondoid crystal, wherein the individual heterodiamondoids in the crystal are held together by Nan der waals (London) forces.
  • a single heterodiamondoid may be used as part of the cathode of a field emission device.
  • n-type diamondoid materials are fabricated using chemical vapor deposition (CND) techniques. Heterodiamondoids may be employed as carbon precursors and as self-contained dopant sources already sp 3 - hybridized in a diamond lattice, using conventional CND techniques.
  • the use of the heterodiamondoids may be used to nucleate a diamond film using conventional CND techniques, where such conventional techniques include thermal CND, laser CND, plasma-enhanced or plasma-assisted CND, electron beam CND, and the like.
  • conventional CND techniques include thermal CND, laser CND, plasma-enhanced or plasma-assisted CND, electron beam CND, and the like.
  • Conventional methods of synthesizing diamond by plasma enhanced chemical vapor deposition (PECND) techniques are well known in the art, and date back to around the early 1980's. Although it is not necessary to discuss the specifics of these methods as they relate to the present invention, one point in particular should be made since it is relevant to the role hydrogen plays in the synthesis of diamond by "conventional" plasma-CND techniques. In one method of synthesizing diamond films discussed by A. Erdemir et al.
  • a modified microwave CND reactor is used to deposit a nanocrystalline diamond film using a C 60 fullerene, or methane, gas carbon precursor.
  • a device called a "quartz transpirator” is attached to the reactor, wherein this device essentially heats a fullerene-rich soot to temperatures between about 550 and 600°C to sublime the C 60 fullerene into the gas phase.
  • a similar device may be used to sublime heterodiamondoids into the gas phase such that they may be introduced to a CND reactor.
  • An exemplary reactor is shown in generally at 600 in FIG. 6.
  • a reactor 600 comprises reactor walls 601 enclosing a process space 602.
  • a gas inlet tube 603 is used to introduce process gas into the process space 602, the process gas comprising methane, hydrogen, and optionally an inert gas such as argon.
  • a diamondoid subliming or volatilizing device 604 similar to the quartz transpirator discussed above, may be used to volatilize and inject a diamondoid containing gas into the reactor 600.
  • the volatilizer 604 may include a means for introducing a carrier gas such as hydrogen, nitrogen, argon, or an inert gas such as a noble gas other than argon, and it may contain other carbon precursor gases such as methane, ethane, or ethylene.
  • a carrier gas such as hydrogen, nitrogen, argon, or an inert gas such as a noble gas other than argon, and it may contain other carbon precursor gases such as methane, ethane, or ethylene.
  • the reactor 600 may have exhaust outlets 605 for removing process gases from the process space 602; an energy source for coupling energy into process space 602 (and striking a plasma from) process gases contained within process space 602; a filament 607 for converting molecular hydrogen to monoatomic hydrogen; a susceptor 608 onto which a diamondoid containing film 609 is grown; a means 610 for rotating the susceptor 608 for enhancing the sp 3 -hybridized uniformity of the diamondoid- containing film 609; and a control system 611 for regulating and controlling the flow of gases through inlet 603; the amount of power coupled from source 606 into the processing space 602; the amount of diamondoids injected into the processing space 602; the amount of process gases exhausted through exhaust ports 405; the atomization of hydrogen from filament 607; and the means 610 for rotating the susceptor 608.
  • the plasma energy source 606 comprises an induction coil such that power is coupled into process gases within processing space 602 to create a plasma 612.
  • a heterodiamondoid precursor may be injected into reactor 600 according to embodiments of the present invention through the volatilizer 604, which serves to volatilize the diamondoids.
  • a carrier gas such as methane or argon may be used to facilitate transfer of the diamondoids entrained in the carrier gas into the process space 602.
  • the injection of such heterodiamondoids provides a method whereby impurity atoms may be inserted into a diamond film without having to resort to crystal damaging techniques such as ion implantation.
  • the heterodiamondoids may be introduced to the reactor simply by placing them on the substrate onto which the film will be deposited, prior to inserting the substrate into the reactor. It is contemplated in some embodiments that the injected methane gas provides the majority of the carbon material present in a CND created film, with the heterodiamondoid portion of the input gas influencing the rate of growth, crystallographic orientation, and perhaps grain structure, but more importantly, the heterodiamondoid portion of the input gas supplies the heteroatom impurity that will eventually function as the electron donating species in the n-type diamond or diamond-like film. This process is illustrated schematically in FIGS. 7A-7C. Referring to FIG.
  • a substrate 700 is positioned within the CND reactor 600, and a conventional CND diamond film 701 is grown on the substrate 700.
  • This diamond film 701 comprises tetrahedrally bonded carbon atoms, where a carbon atom is represented by the intersection of two lines in FIG. 7A-C, such as depicted by reference numeral 702, and a hydrogen terminated surface represented by the end of a line, as shown by reference numeral 703.
  • the hydrogen passivated surface 703 of the diamond film 701 is very important. Hydrogen participates in the synthesis of diamond by PECND techniques by stabilizing the sp 3 bond character of the growing diamond surface. As discussed in the reference cited above, A. Erdemir et al.
  • a heterodiamondoid 704 is injected in the gas phase into the CND reactor via the volatilizing device 604 described above.
  • the heterodiamondoid 704 has tetrahedrally bonded carbon atoms at the intersections of lines 702, as well as a hydrogen passivated surface at the end of the lines 703, as before.
  • the heterodiamondoid 704 also has a heteroatom 705 substitutionally positioned within its lattice structure, and the heteroatom may be an electron donor or acceptor.
  • the heterodiamondoid 704 is deposited on the surface of the CND diamond film 701, as shown in FIG. 7B.
  • the carbon atoms of the heterodiamondoid 704 become tetrahedrally coordinated with (bonded to) the carbon atoms of the film 701 to produce a continuous diamond lattice structure across the newly created interface of the heterodiamondoid 704 and the diamond film 701.
  • the result is a diamond film 707 having an impurity atom (which may be an electron donor or acceptor) substitutionally positioned on a lattice site position within the diamond crystal structure, as shown in FIG. 7C. Since the heterodiamondoid has been incorporated into the growing diamond film, so has its heteroatom become incorporated into the growing film, and the heteroatom has retained its sp -hybridization characteristics through the deposition process.
  • the weight of heterodiamondoids and substituted heterodiamondoids may in one embodiment range from about 1 part per million (ppm) to 10 percent by weight. In another embodiment, the content of heterodiamondoids and substituted heterodiamondoids is about 10 ppm to 1 percent by weight.
  • the proportion of heterodiamondoids and substituted heterodiamondoids in the CND film relative to the total weight of the film is about 100 ppm to 0.01 percent by weight.
  • heterodiamondoids may be assembled into n- type materials by polymerization. For this to occur, it is necessary to derivatize (or functionalize) the heterodiamondoids prior to polymerization, and methods of forming diamondoid derivatives, and techniques for polymerizing derivatized diamondoids, are discussed in U.S. patent application Serial Number 10/046,486, entitled “Polymerizable Higher Diamondoid Derivatives," by Shenggao Liu, Jeremy E. Dahl, and Robert M.
  • SNI -type reactions involve the generation of heterodiamondoid carbocations, which subsequently react with various nucleophiles. Since tertiary (bridgehead) carbons of heterodiamondoids are considerably more reactive than secondary carbons under S N I reaction conditions, substitution at a tertiary carbon is favored. S E -type reactions involve an electrophilic substitution of a C-H bond via a five-coordinate carbocation intermediate. Of the two major reaction pathways that may be used for the functionalization of heterodiamondoids, the S N I -type may be more widely utilized for generating a variety of heterodiamondoid derivatives.
  • Mono and multi-brominated heterodiamondoids are some of the most versatile intermediates for functionalizing heterodiamondoids. These intermediates are used in, for example, the Koch-Haaf, Ritter, and Friedel-Crafts alkylation and arylation reactions. Although direct bromination of heterodiamondoids is favored at bridgehead (tertiary) carbons, brominated derivatives may be substituted at secondary carbons as well. For the latter case, when synthesis is generally desired at secondary carbons, a free radical scheme is often employed. Although the reaction pathways described above may be preferred in some embodiments of the present invention, many other reaction pathways may certainly be used as well to functionalize a heterodiamondoid.
  • reaction sequences may be used to produce derivatized heterodiamondoids having a variety of functional groups, such that the derivatives may include heterodiamondoids that are halogenated with elements other than bromine (e.g. fluorine), alkylated diamondoids, nitrated diamondoids, hydroxylated diamondoids, carboxylated diamondoids, ethenylated diamondoids, and aminated diamondoids.
  • elements other than bromine e.g. fluorine
  • alkylated diamondoids e.g. fluorine
  • nitrated diamondoids e.g. hydroxylated diamondoids
  • carboxylated diamondoids ethenylated diamondoids
  • aminated diamondoids e.g.
  • Heterodiamondoids, as well as heterodiamondoid derivatives having substituents capable of entering into polymerizable reactions may be subjected to suitable reaction conditions such that polymers are produced.
  • the polymers may be homopolymers or heteropolymers, and the polymerizable diamondoid and/or heterodiamondoid derivatives may be co-polymerized with nondiamondoid, diamondoid, and/or heterodiamondoid-containing monomers.
  • Polymerization is typically carried out using one of the following methods: free radical polymerization, cationic, or anionic polymerization, and polycondensation.
  • Free radical polymerization may occur spontaneously upon the absorption of an adequate amount of heat, ultraviolet light, or high-energy radiation. Typically, however, this polymerization process is enhanced by small amounts of a free radical initiator, such as peroxides, aza compounds, Lewis acids, and organometallic reagents. Free radical polymerization may use either non-derivatized or derivatized heterodiamondoid monomers.
  • the functional groups comprising substituents on a diamondoid or heterodiamondoid may polymerize such that the diamondoids or heterodiamondids end up being attached to the main chain as side 5/076825 - 25 -
  • Diamondoids and heterodiamonhdoids having more than one functional group are capable of cross-linking polymeric chains together.
  • a cationic catalyst may be used to promote the reaction. Suitable catalysts are Lewis acid catalysts, such as boron trifluoride and aluminum trichloride. These polymerization reactions are usually conducted in solution at low-temperature.
  • anionic polymerizations the derivatized diamondoid or heterodiamdondoid monomers are typically subjected to a strong nucleophilic agent. Such nucleophiles include, but are not limited to, Grignard reagents and other organometallic compounds. Anionic polymerizations are often facilitated by the removal of water and oxygen from the reaction medium.
  • Polycondensation reactions occur when the functional group of one diamondoid or heterodiamondoid couples with the functional group of another; for example, an amine group of one diamondoid or heterodiamondoid reacting with a carboxylic acid group of another, forming an amide linkage.
  • one diamondoid or heterodiamondoid may condense with another when the functional group of the first is a suitable nucleophile such as an alcohol, amine, or thiol group, and the functional group of the second is a suitable electrophile such as a carboxylic acid or epoxide group.
  • heterodiamondoid-containing polymers examples include polyesters, polyamides, and poly ethers.
  • a synthesis technique for the polymerization of heterodiamondoids comprises a two-step synthesis.
  • the first step involves an oxidation to form at least one ketone functionality at a secondary carbon (methylene) position of a heterodiamondoid.
  • the heterodiamondoid may be directly oxidized using a reagent such as concentrated sulfuric acid to produce a keto- heterodiamondoid. In other situations, it may be desirable to convert the hydrocarbon to an alcohol, and then to oxidize the alcohol to the desired ketone.
  • the heterodiamondoid may be initially halogenated (for example with N-chlorosuccinimide, NCS), and the resultant halogenated diamondoid reacted with base (for example, KHCO 3 or NaHCO 3 , in the presence of dimethyl sulfoxide).
  • base for example, KHCO 3 or NaHCO 3
  • the second step consists of the coupling two or more keto- heterodiamondoids to produce the desired polymer of heterodiamondoids. It is known in the art to couple diamondoids by a ketone chemistry, and one process has been described as the McMurry coupling process in U.S.
  • coupling may be effected by reacting the keto-heterodiamondoids in the presence of TiCl 3 , Na, and 1,4-dioxane.
  • polymers of diamondoids (adamantanes) have been illustrated in Canadian Patent Number 2100654.
  • keto-heterodiamondoids may be prepared with a diversity of configurational, positional, and stereo configurations.
  • a three step procedure may be useful.
  • This procedure comprises chlorinating an intermediate coupled polymeric heterodiamondoid with a selective reagent such as NCS.
  • NCS a selective reagent
  • the chloro-derivative is convertable to the desired ketone by substitution of the chlorine by a hydroxyl group, and further oxidation by a reagent such as sodium bicarbonate in dimethylsulfoxide (DMSO). Additional oxidation may be carried out to increase ketone yields, the additional treatment comprising further treatment with pyridine chlorochromate (PCC).
  • PCC pyridine chlorochromate
  • FIG. 8 A A schematic illustration of a polymerization reaction between heterodiamondoid monomers is illustrated in FIG. 8 A.
  • a heterodiamondoid 800 is oxidized using sulfuric acid to the keto-heterodiamondoid 801.
  • the particular diamondoid shown at 801 is a tetramantane, however, any of the diamondoids described above are applicable.
  • the symbol "X" represents a heteroatom substitutionally positioned on a lattice site of the diamondoid.
  • the ketone group in this instance is attached to position 802.
  • Two heterodiamondoids 801 may be coupled using a McMurry reagent as shown in step 802.
  • the coupling between two adjacent heterodiamondoids may be made between any two carbons of each respective heterodiamondoid's nuclear structure, and in this exemplary situation the coupling has been made between carbons 803 of diamondoid 806 and carbon 804 of heterodiamondoid 806. It will be apparent to those skilled in the art that this process may be continued; for example, the pair of heterodiamondoids shown generally at 807 may be functionalized with ketone groups on the heterodiamondoids 805 and 806, respectively, to produce the intermediate 808, where two intermediates 808 may couple to form the complex 809.
  • a polymer may be constructed using the individual heterodiamondoids 800 such that n-type material is fabricated. Such a material is expected to be electrically conducting due to the pi-bonding between adjacent heterodiamondoid monomers.
  • individual heterodiamondoid molecules may be coupled with electrically conductive polymer "linkers" to generate an 77-type heterodiamondoid material.
  • a linker is defined as a short segment of polymer comprising one to ten monomer segments of a larger polymer.
  • the linkers of the present invention may comprise a conductive polymer such that electrical conductivity is established between adjacent heterodiamondoids in the overall bulk material.
  • Polymers with conjugated pi-electron backbones are capable of displaying these electronic properties.
  • Conductive polymers are known, and the technology of these materials have been described in a chapter titled "Electrically Conductive Polymers” by J.E. Frommer and R.R. Chance in High Performance Polymers and Composites, J.I. Kroschwitx, Ed. (Wiley, New York, 1991), pp. 174 to 219. The conductivity of many of these polmers have been described in this chapter, and compared to metals, semiconductors, and insulators.
  • a typical semiconducting polymer is poly(p-phenylene sulfide), which has a conductivity as high as 10 3 Siemens/cm 2 (these units are identical to ⁇ cm "1 ), and as low as 10 "15 , which is as insulating as nylon.
  • Polyacetylene is more conducting with an upper conductance of 10 3 ⁇ cm "1 , and a lower conductance of about 10 "9 ⁇ cm "1 .
  • heterodiamondoids may be electrically connected to form a bulk n-type material using oligomers of the polymers discussed above.
  • an oligomer refers to a polymerization of about 2 to 20 monomers.
  • an oligomer may be thought of as a short polymer.
  • the purpose of the oligomers, and/or linkers is to electrically connect a number of heterodiamondoids into a three-dimensional structure such that a bulk material having p-type or n-type electrical conductivity may be achieved.
  • Conductive polymers have been discussed in general by J.E. Frommer and R.R. Chance in a chapter titled “Electrically conductive polymers," in High Perfoi'mance Polymers and Composites, J.I. Kroschwitz, ed. (Wiley, New York, 1991), pp. 174-219.
  • Typical linkers that have been shown to be electrically conductive are polyacetylene in FIG. 9A, polythiophene in FIG. 9E, and polyparaphenylene vinylene in FIG. 9F.
  • An electrically conductive linker that will be highlighted as an example in the next discussion is polyaniline, the oligomer of which has been depicted in FIG. 9N.
  • a schematic diagram of a heterodiamondoid polymer generated with polyaniline linking groups is depicted in FIG. 10.
  • the polymer of FIG. 10 is only exemplary in that the conductive linker groups between adjacent heterodiamondoids is a polyaniline functionality, but of course the linking group could be any conductive polymer, many of which comprise conductive diene systems.
  • a heterodiamondoid 1001 is linked to a heterodiamondoid 1002 via a short segment 5/076825
  • the polymer shown generally at 1000 may also contain crosslinks that connect a linear chain 1006 with 1007. This creates a three-dimensional crosslinked polymer with electrical conductivity in a three-dimensional sense.
  • Crosslinked chains 1008 may be used to connect adjacent linear chains 1006 and 1007. A three- dimensional matrix of an electrically conducting diamondoid containing material is thus established.
  • Each heterodiamondoid 1001 and 1002 contains within its structure a heteroatom which is either an electrical donor or electrical accepter. Overall, fabrication of an n-type heterodiamondoid material is achieved.
  • a third method of fabricating 77-type materials is crystallize the heterodiamondoids into a solid, where the individual heterodiamondoids comprising the solid are held together by Nan der Waals forces (also called London or dispersive forces). Molecules that are held together in such a fashion have been discussed by J.S. Moore and S. Lee in “Crafting Molecular Based Solids,"
  • molecular solids Chemistry and Industry, July, 1994, pp. 556-559, and are called "molecular solids" in the art. These authors state that in contrast to extended solids or ionic crystals, the prefered arrangement of molecules in a molecular crystal is presumably one that minimizes total free energy, and thus the fabrication of a molecular crystal is controlled by thermodynamic considerations, unlike a synthetic process.
  • An example of a molecular crystal comprising the pentamantane [1(2,3)4] will be discussed next.
  • a molecular crystal comprising [1(2,3)4] pentamantane was formed by the chromatographic and crystallographic techniques described above.
  • This diagram illustrates the generalized manner in which diamondoids may pack in order to be useful according to embodiments of the present invention.
  • These molecular crystals display well-defined exterior crystal facets, and are transparent to visible radiation.
  • the packing of the [1(2,3)4] pentamantane is illustrated as a stero view of two unit cells 1102 and 1103.
  • Each unit cell of the crystal contains four pentamantane molecules, where the molecules are arranged such that there is one central cavity or pore per unit cell.
  • the cavity 1106 that is created by the packing of the pentamantane unit cells may accommodate small impurities, or may be enlarged to accomodate a transition element metal such as gold.
  • the purpose of including such impurities may be to enhance electrical conductivity.
  • One significant feature of the packing of the [1(2,3)4] pentamantanes illustrated in FIG. 11 is that ap or «-type diamondoid material may be realized with little further processing than isolation using chromatographic techniques. In other words, no functionalization is necessary to polymerize or link up individual diamondoid molecules, and no expensive deposition equipment is needed in this embodiment. Since these crystal are mechanically soft and easily compressible, being held together by Nan der Waals forces, an exterior "mold" may be necessary to support the ⁇ -type, electron donating material.
  • the mold may comprise, for example, regions of sp 2 -hybridized carbon materials.
  • a heterodiamondoid (or small cluster of several heterodiamonoids) is contemplated to function at a molecular level as quantum devices such in, for example, single electron emitters.
  • Single electron devices are known, and single electron transistors have been discussed in the art. See, for example, U.S. Pat. 6,335, 245, issued to Park et al., and Quantum Semiconductor Devices and Technologies, T.P Pearsall, ed. (Kluwer, Boston, 2000), pp. 8-12.
  • Park discloses that efforts to reduce device size in the semiconductor industry will drive a reduction in the number of electrons present in a channel (e.g., the conducting pathway between the source and drain of a transistor) from about 300 in the year 2010 to no more than 30 in the year 2020. As the number of electrons necessary for operating a device is reduced, statistical variations in electron behavior will become more of a concern.
  • a channel e.g., the conducting pathway between the source and drain of a transistor
  • FIG. 12 An example of a heterodiamondoid contemplated for use in a single electron emitter is shown in FIG. 12.
  • an /z-type heterodiamondoid comprising a tetramantane 1201 with nitrogen heteroatoms is coupled to a similar tetramantane 1202 through a carbon-carbon double bond 1208 as discussed in the polymer section above.
  • the number of heterodiamondoid molecules in this complex may range from about 1 to 10,000.
  • the electron-emitter contemplated by the present embodiments is not restricted to «-type materials. In other words, the emitter (the cathode of the FED) may comprise p- ype materials as well.
  • The/?-type materials act as electron acceptors, and it is desirable to have the number of electron-donating elements greater than the number of electron-accepting elements such that overall, the material is electron-donating. Inclusion of electron-accepting elements in the emitter material is contemplated, in some situations, to give an enhanced control over the number and distribution of the electrons actually emitted.
  • a p-type tetramantane 1203 with boron heteroatoms may be coupled to a similar tetramantane 1204 through a carbon-carbon double bond 1209.
  • the complex of n-type diamondoids 1205 may be coupled to the complex ofp-type diamondoids 1206 to form the complex 1207.
  • Such a molecular complex may function as a single electron emitter.
  • the heterodiamondoids of the present invention offer enhanced reliability, controllability, and reproducibility not available with prior art methods.
  • Properties of n-type diamond To date, the well-known impurity atoms that have been used to dope diamond include boron and nitrogen. Boron is a -type dopant with an activation energy of 0.37 eN. Nitrogen is an 77-type impurity which may be referred to as a deep donor, because it has the energy level 1.7 eN away from the bottom of the conduction band.
  • boron is the best studied p-type dopant in diamond.
  • the boron doped materials demonstrate hole mobilities up to 600 cmVN s, and compensation ratios below 5 percent.
  • the optimal annealing scheme was found to be a high temperature anneal at a temperature greater than 1400°C.
  • 72-type diamond has been more difficult to fabricate.
  • nitrogen and phosphorus appear to enter the crystal to contribute to its electrical properties. Both elements may be introduced into diamond during CND growth.
  • group I elements occupying interstitial sites such as sodium and lithium have been predicted to act as donors with activation energies of 0.1 and 0.3 eN, respectively.
  • the energy of formation for the bonding of nitrogen within the carbon lattice is predicted to be negative, -3.4 eN, in contrast to the high positive energies of formation predicted for phosphorus (10.4 eN), lithium (5.5 eN), and sodium (15.3 eN). This suggests that the solubilities of these elements in diamond is low, with the exception of nitrogen.
  • nitrogen also exists substitutionally in natural diamond (type lb diamond), where the impurity has an activation energy of 1.7 eN.
  • the cause was speculated to be the large size of the phosphorus atom relative to the dimensions of the diamond crystal lattice.
  • the misfit induces a strain in the diamond lattice which appears to attract and create defects with no electrical activity.
  • Attempts have also been made to produce ⁇ -type diamond by lithium implantation.
  • 7z-type conductivity was verified by hot probe measurements, with an activation energy of 0.23 eN.
  • Another study found an activation energy of 0.22 eN.
  • about 40 percent of the implanted lithium was found to occupy interstitial lattice sites, with 17 percent in substitutional sites, but no clear n-type electrical signal could be found in this case.
  • the average crystallite size was reduced by an order of magnitude when the boron concentration was increased from about 10 16 to 10 21 cm “3 .
  • Such a technique has been discussed by G.Z. Cao in chapter B3.4, titled “Nitrogen and phosphorus doping in CND diamond," in Properties, Growth and Applications of Diamond, edited by M. H. ⁇ azare and A. J. ⁇ eves (Inspec, London, 2001), pp. 345-347. This author states that diamond promises high power, high frequency, and high temperature electronic applications due to its unique physical properties.
  • Typical concentrations were 6 x 10 19 atoms/cm 3 .
  • the rate of incorporation of nitrogen into the growing diamond film was dependent on the orientation of the growing film, and the growth rate of the film was dependent on the amount of nitrogen in the feed gas.
  • (100) facets incorporated the highest concentration of nitrogen into the diamond, followed by (111) facets, with (100) facets incorporating the least amount of nitrogen.
  • the addition of nitrogen to the feed gas resulted in the greatest enhancement of growth for (100) facets, followed by (111) facets, with the least enhancement in (110) facets.
  • phosphorus is a promising donor candidate for n-type semiconducting diamond films.
  • phosphorus may behave as a shallow donor in diamond, having an energy level 0.2 eN from the bottom of the conduction band.
  • phosphorus has a large positive energy of formation (10.4 eN), and thus a low equilibrium solubility in diamond. This is in part due to the large size of phosphorus relative to carbon; for example, phosphorus has a radius of 1.10 angstroms compared to the 0.77 angstrom radius of carbon.
  • concentrations of phosphorus could be enhanced in the presence of other impurities, such as boron.
  • the properties of of the doped diamond depend on the nature of the dopant. Boron doped diamond has an acceptor level of 0.368 eN above the valence band, which may be viewed as a shallow level, and therefore holes may be excited from states within the bandgap to the top of the valence band with relatively low energies. However, nitrogen is a deep donor with an energy level 1.7 eN away from the bottom of the conduction band, and therefore relatively large amounts of energy are required to elevate an electron from a donor state within the conduction band to the bottom of the conduction band.
  • 7j-type diamond when 7j-type diamond is doped with diamond, it is not electrically conducting at room temperature because these temperature do not provide enough energy to excite the electron from its energy state state within the bandgap to the conduction band.
  • Phosphorus has been modelled to be a shallow donor with an energy state at 0.2 eN away from the conduction band edge, making phosphorus a potential candidate for an n-type dopant, and lithium is another possiblity.
  • the hydrogenated surface of diamond may impart to the crystal a/7-type conductivity. This has been discussed by K. Bobrov et al. in "Atomic-scale imaging of insulating diamond through resonant electron injection," Nature, Nol. 413, pp.
  • a heterodiamondoid or heterodiamondoid-containing material is utilized as a cold cathode filament in a field emission device suitable for use, among other places, in flat panel displays.
  • the unique properties of a heteroatom-containing diamondoid make this possible. These properties include the negative electron affinity of a hydrogenated diamond surface, in conjunction with the small size of a typical higher diamondoid molecule.
  • the latter presents striking electronic features in the sense that the diamond material in the center of the diamondoid comprises high purity diamond single crystal, with the existence of significantly different electronic states at the surface of the diamondoid. These surface states may make possible very long diffusion lengths for conduction band electrons.
  • An electron-donating heteroatom such as nitrogen for example, contributes electrons to the conduction band of the material to facilitate electron emission from the cathode.
  • An electron-donating heteroatom such as nitrogen for example, contributes electrons to the conduction band of the material to facilitate electron emission from the cathode.
  • Diamonds in general, and in particular a hydrogenated diamond surface offer a unique solution to this problem because of the fact that a diamond surface displays an electron affinity that is negative.
  • the electron affinity of the material is a function of electronic states at the surface of the material.
  • the energy barrier to an electron attempting to escape the material is energetically favorable and in a "downhill" direction.
  • Diamond is the only known material to have a negative electron affinity in air.
  • the electron affinity ⁇ of a material is negative, where ⁇ is defined to be the energy required to excite an electron from an electronic state at the minimum of the conduction band to the energy level of a vacuum.
  • the minimum of the conduction band is below that of the vacuum level, so that the electron affinity of that material is positive.
  • Electrons in the conduction band of such a material are bound to the semiconductor by an energy that is equal to the the electron affinity, and this energy must be supplied to the semiconductor to excite and electron from the surface of that material.
  • a field emission cathode comprising a diamond filament may suffer from an inherent property: while electrons in the conduction band are easily ejected into the vacuum level, exciting electrons from the valence band into the conduction band to make them available for field emission may be problematic. This is because of the wide bandgap of diamond. In a normal situation, few electrons are able to traverse the bandgap, in other words, move from electronic states in the valence band to electronic states in the conduction band. Thus, diamond is generally thought to be unable to sustain electron emission because of its insulating nature.
  • a field emission cathode comprises a heterodiamondoid, a derivatized heterodiamondoid, a polymerized heterodiamondoid, and all or any of the other diamondoid containing materials discussed in previous sections of this description.
  • the heteroatom of the heterodiamondoid is an electron-donating species such as nitrogen.
  • An exemplary field emission cathode comprising a heterodiamondoid is shown in FIG. 13.
  • a field emission device shown generally at 1300 comprises a heterodiamondoid-containing filament 1301, which acts as a cathode for the device 1300, and a faceplate 1302 on which a phosphorescent coating 1303 has been deposited.
  • the anode for the device may be either a conductive layer 1304 positioned behind the phosphorescent coating 1303, or an electrode 1305 positioned adjacent to the filament 1301.
  • a voltage from a power supply 1306 is applied between the filament electrode 1307, and the anode of the device, either electrode 1304 or 1305.
  • a typical operating voltage (that is, the potential difference between the cathode and the anode) is less than about 10 volts. This is what allows the cathode to be operated in a so-called "cold" configuration.
  • a typical electronic affinity for a diamondoid surface is contemplated to be less than about 3 eN, and in other embodiments it may be negative.
  • the heterodiamondoid filament (or cathode) 1301 contains an electron- donating heteroatom 1310, which may be any column N (TUPAC notation) or column NI element such as ⁇ , P, As, or O, S, Se, respectively. These electron- donating elements contribute one electron (for the column N case) or two electrons (for the column NI case) to the conduction band of the material comprising the heterodiamondoid-containing cathode.
  • TUPAC notation column N
  • column NI element such as ⁇ , P, As, or O, S, Se
  • the cathode may be dimensionally small enough to allow electrons to tunnel (in a quantum mechanical sense) from the filament electrode 1307 to an opposite surface of the heterodiamondoid, which may be the surface 1308 or the tip 1309. It will be appreciated by the skilled in the art that it is not essential for the heterodiamondoid filament 1301 to have an apex or tip 1309, since the surface of the diamondoid is hydrogenated and sp 3 -hybridized.
  • the surface of the cathode 1301 may comprise a heterodiamondoid-containing material that is at least partially derivatized such that the surface comprises both sp 2 and sp 3 -hybridization.
  • the electron affinity of the cathode is less than about 3 eN, and may be negative.
  • Tthe heterodiamondoid content of the cathode 1301 may range from about 1 to 100 percent by weight for the heterodiamondoid-containing component, whether the heterodiamondoid-containing component is a product of a CND reaction, a polymer, a molecular crystal, or a cluster of individual heterodiamondoids.
  • the form of the heterodiamondoid-containing material may include fiber or film shapes.
  • the surface of the heterodiamondoid-containing material may comprise carbon atoms that are substantially sp 3 -hybridized, but the surface may also be derivatized or co-crystallized such that the surface comprises both sp 2 and sp 3 -hybridized carbon.
  • An advantage contemplated by this embodiment of the present invention is that a greater resolution of the device may be realized relative to a conventional field emission device because of the greater number of electrons that may be emitted, the small size of a typical heterodiamondoid, and the more repeatable and uniform structure available with the use of heterodiamondoids.
  • Examples 1-3 describe methods that could be used to prepare nitrogen containing heterodiamondoids; e.g. azadiamondoids.
  • Example 4 discloses exemplary methods of preparing polymers from heterodiamondoids, including polymers comprising heterodiamondoids coupled through double bonds between diamondoid lattice site carbons.
  • Example 1 demonstrate the preparation of aza tetramantanes from a feedstock which contains a mixture of tetramantanes including some alkyltetramantanes and other impurities.
  • Other feedstocks containing different diamondoids such as triamantane, or tetramantane and higher diamondoids may also be applicable and produce similar heterodiamondoid mixtures.
  • Example 1 Aza tetramantanes from a feedstock containing a mixture of tetramantane isomers
  • a mixture of aza tetramantanes was prepared from a feedstock containing a mixture of the three tetramantane isomers wo-tetramantane, ⁇ ntz-tetramantane, and s/ ew-tetramantane.
  • a first step in this exemplary synthesis involved the photo-hydroxylation of a feedstock containing tetramantanes.
  • the feedstock may be obtained by methods described in U.S. Patent Application 10/052,636, filed January 17, 2002, and incorporated herein by reference in its entirety.
  • a fraction containing at least one of the tetramantane isomers was obtained, and the fraction may have included substituted tetramantanes (such as an alkyltetramantane) and hydrocarbon impurities as well.
  • the gas chromatagraphy/mass spetrometry (GC/MS) of the composition of this fraction showed a mixture of tetramantanes.
  • a solution of 200 mg of the above feedstock containing tetramantanes in 6.1 g of methylene chloride was mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate.
  • the solution While being stirred vigorously, the solution was irradiated with a 100-watt UN light. Gas evolution was evident from the start. The temperature was maintained at 40-45°C for an irratiation period of about 21 hours. Then the solution was concentrated to near dryness, treated twice in succession with 10-mL portions of toluene, and reevaporated to dryness. The product was then subjected to GC/MS characterization to show the presence of hydroxylated tetramantane isomers.
  • the tetramantane feedstock may be oxidized directly according to the procedures of McKervey et al. (see J. Chem. Soc, Perkin Trans. 1, 1972, 2691).
  • the crude product mixture is then subjected to GC/MS characterization to show the presence of iso-tetramantones.
  • the oxidized feedstock as prepared by direct oxidation, wherein the product contains tetramantones, is then reduced with lithium aluminum hydride in ethyl ether at a low temperature.
  • the reaction mixture is worked up by adding saturated ⁇ a 2 SO 4 aqueous solution to decompose excess lithium aluminum hydride at a low temperature. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude product.
  • the crude product may be characterized by GC/MS to show the presence of hydroxylated tetramantane isomers.
  • an azahomo tetramantane-ene may be produced from the above hydroxylated tetramantanes, or from photooxidized tetramantanes.
  • a simpler reaction product was obtained if the reaction was allowed to proceed for only a short time; longer periods gave a complex mixture.
  • the initial product was characterized by GC/MS as a mixture of N-formyl aza tetramantanes.
  • aza tetramantanes was prepared from the above described N- formyl aza tetramantanes by mixing the N-formyl aza tetramantanes with 10 mL of 15% hydrochloric acid. The resultant mixture was heated to a boil for about 24 hours. After cooling, the mixture was subjected to a typical workup to afford a product which was characterized by GC/MS showing the presence of aza tetramantanes.
  • Example 2 Preparation of aza iso-tetramantane from iso-tetramantane
  • an aza wo-tetramantane is prepared from a single tetramantane isomer, wo-tetramantane, as shown in FIGS. 5A-B.
  • this synthetic pathway also begins with the photo- hydroxylation of zso-tetramantane or chemical oxidation/reduction to the hydroxylated compound 2a shown in FIG. 5 A.
  • a solution of 3.7 mmol wo-tetramantane in 6.1 g of methylene chloride is mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate. While stirring vigorously, the solution is irradiated by a 100-watt UN light, and gas evolution is evident as soon as the irridation process is started. The temperature is maintained at 40-45 °C for an irradiation period of about 21 -hours. The solution is then concentrated to near dryness, treated twice in succession with 10-mL portions of toluene, and reevaporated to dryness.
  • the crude product containing a mixture of iso-tetramantanes hydroxylated at the C-2 and C-3 positions is not purified; instead, the mixture is used directly in a reaction comprising the oxidation of the hydroxylated compound 2 a to a keto compound 1.
  • the photo-hydroxylated tsO-tetramantane containing a mixture of C-2 and C- 3 hydroxylated i-o-tetramantanes is partially dissolved in acetone.
  • the oxygenated components go into solution, but not all of the unreacted t,sO-tetram.antane is capable of being dissolved.
  • a solution of chromic acid and sulfuric acid is then added dropwise until an excess of the acid is present, and the reaction mixture is stirred overnight.
  • the acetone solution is decanted from the precipitated chromic sulfate and unreacted iso-tetramantane, and dried with sodium sulfate.
  • the unreacted iso- tetramantane is recovered by dissolving the chromium salts in water with subsequent filtering. Evaporation of the acetone solution affords a white solid.
  • the crude solid is chromatographed on alumina using conventional procedures, where it may be eluted initially with 1 : 1 (v/v) benzene/light petroleum ether followed by either ethyl ether or by a mixture of ethyl ether and methanol (95:5 v/v), in order to collect first the unreacted wo-tetramantane and then the keto compound 1. Further purification by recrystallization from cyclohexane may afford a substantially pure product 1. Alternatively, w ⁇ -tetramantane may be directly oxidized to the keto compound 1 according to the procedures of McKervey et al. (J. Chem. Soc, Perkin Trans. 1, 1972, 2691).
  • the ketone compound 1 may be reduced to a C-2 hydroxylated wo-tetramantane 2a by treating the ketone compound 1 with excess lithium aluminum hydride in ethyl ether at low temperatures. After completion of the reaction, the reaction mixture is worked up by adding at a low temperature a saturated ⁇ a 2 SO 4 aqueous solution to decompose the excess hydride. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude monohydroxylated iso-tetramantane substituted at the secondary carbon. This compound may be described as a C-2 tetramantan-ol.
  • a C-2 methyl hydroxyl iso-tetramantane 2b may be prepared from the keto compound 1 by adding dropwise to a stirred solution of keto compound 1 (2 mmol) in dry THF (20 mL) at -78 °C (dry ice/methanol) a 0.8 molar solution (2.8 mL, 2.24 mmol) of methyllithium in ether. The stirring is continued for about 2 hours at -78°C, and for another 1 hour at room temperature. Then, saturated ammonium chloride solution (1 mL) is added, and the mixture extracted with ether (2x30 mL).
  • the azahomo wo-tetramantane-ene 3 is prepared from the hydroxylated compound 2.
  • methanesulfonic acid 15 mL
  • dichloromethane 10 mL
  • solid sodium azide 1.52 g, 8.0 mmol
  • sodium azide 1.04 g, 16 mmol
  • the stirring is continued for about 8 hours at about 20 to 25°C.
  • the mixture is then poured onto ice water (ca. 10 mL). The aqueous layer is separated, washed with
  • a mixture of the azahomo zsO-tetramantane-ene 3 (3a or 3b) with 7W-CPBA (1.1 equ.) in CH 2 Cl 2 -NaHCO 3 is stored at 5-20°C, followed by the usual workup and short column chromatography gives the epoxy azahomo wo-tetramantane 4 (4a or 4b).
  • N-acyl aza wo-tetramantane 5b is prepared from the epoxy azahomo wo-tetramantane 4b by irradiating the epoxy azahomo zs ⁇ -tetramantane 4b in cyclohexane for about 0.5 hours with a UN lamp.
  • ⁇ -formyl aza 5a can be similarly prepared from the epoxy azahomo ts ⁇ -tetramantane 4a.
  • the aza ts ⁇ -tetramantane 6 is prepared from ⁇ -acyl aza- isotetramantane 5b by heating the ⁇ -acyl aza zso-tetramantane 5b (5 mmol) to reflux for about 5 hours with a solution of 2 g powdered sodium hydroxide in 20 mL diethylene glycol. After cooling, the mixture is poured into 50 mL water and extracted with ethyl ether. The ether extract is dried with potassium hydroxide. The ether is distilled off to afford the product aza ts ⁇ -tetramantane 6.
  • the hydrochloride salt is generally prepared for analysis.
  • dry hydrogen chloride is passed into the ether solution of the amine, whereby the salt separates out as a crystalline compound.
  • the salt may be purified by dissolving it in ethanol, and precipitating with absolute ether. Typically, the solution is left undisturbed for several days to obtain complete crystallization.
  • the aza tsO-tetramantane 6 may be prepared from the ⁇ -formyl aza ts ⁇ -tetramantane 5a by mixing the ⁇ -formyl aza zs ⁇ -tetramantane 5a (2.3 mmol) with 10 mL of 15% hydrochloric acid. The resultant mixture is heated to a boil for about 24 hours.
  • Example 3 Preparation of the aza iso-tetramantane 6 product by fragmentation of a keto compound 1 to an unsaturated carboxylic acid 7
  • An alternative synthetic pathway for the preparation of the product aza iso- tetramantane 6 is shown in FIG. 5B.
  • the w ⁇ -tetramantone 1 as prepared above may be fragmented to the unsaturated carboxylic acid 7 by an abnormal Schmidt reaction per McKervey et al. (Synth. Comrnun., 1973, 3, 435).
  • the compound 8 may be prepared from the carboxylic acid 7. To 4.6 mmol of the carboxylic acid 7 is added 12 mL of glacial acetic acid and 3.67 g (4.48 mmol) of anhydrous sodium acetate. The mixture is stirred and heated to about 70°C.
  • Compound 9 (exo- or endo-) may then be prepared from compound 8 (exo- or endo-) by adding to a solution of compound 8 (0.862 mmol) in 5 mL of anhydrous ether 0.13 g (3.4 mmol) of lithium aluminum hydride. The mixture is refluxed with stirring for about 24 hours. Excess lithium aluminum hydride is destroyed by the dropwise addition of water, and the precipitated lithium and aluminum hydroxides are dissolved in excess 10% hydrochloric acid.
  • the orange solution is then stirred at 25°C for an addition period of about 3 hours. Most of the acetone is removed, and 5 mL of water is added to the residue. The aqueous mixture is extracted twice with ether, and the combined extracts are washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, and evaporated to give crude compound 10. Sublimation on a steam bath gives substantially pure 10.
  • the compound 10 may be prepared from an individual isomer of the compound 9, as opposed to the mixture of exo- and endo-9 isomers.
  • compound 10 may be prepared from exo-9 by stirring a solution of exo-9 (1.05 mmol) in 5 mL of acetone in an Erlenmeyer flask at 25°C. To this solution is added dropwise 8 N chromic acid until the orange color persists, the temperature being maintained at about 25°C. The orange solution is then stirred at 25°C for about 3 hours. Most of the acetone is removed, and 5 mL of water is added to the residue. The aqueous mixture is extracted twice with ether, and the combined extracts are washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, and evaporated to give crude 10. Sublimation on a steam bath gives substantially pure 10.
  • compound 10 may be prepared directly from the carboxylic acid 7, rather than through intermediate compounds 8 and 9.
  • a solution of the carboxylic acid 7 (4.59 mmol) in 15 mL of dry THF is stirred under dry argon and cooled to 0°C.
  • a solution of 1.5 g (13.76 mmol) of lithium diisopropylamide in 25 mL of dry THF under argon is added through a syringe to the solution of 7 at such a rate that the temperature does not rise above about 10°C.
  • the resulting solution of the dianion of 7 is stirred at 0 °C for about 3 hours.
  • compound 11 may be prepared from compound 10 in the following manner. To a solution of compound 10 (1.6 mmol) in a mixture of pyridine and 95% ethanol (1:1) is added 250 mg (3.6 mmol) of hydroxylamine hydrochloride, and the mixture is stirred at reflux for about 3 days. Most of the solvent is evaporated in a stream of air, and the residue is taken up in 25 mL of water. An ether extract of the aqueous solution is washed with 10% HC1 to extract the oxime 11. Neutralization of the acid wash with 10% sodium hydroxide precipitate the oxime 11, which is filtered off and recrystallized from ethanol- water.
  • the aza w ⁇ -tetramantane 6 is prepared from compound 11 by the dropwise addition of a solution of compound 11 (0.98 mmol) in 25 mL of anhydrous ether to a stirred suspension of 250 mg (6.58 mmol) of lithium aluminum hydride in 25 mL of anhydrous ether. The mixture is stirred at reflux for about 2 days. Excess lithium aluminum hydride is destroyed with water, and the precipitated lithium and aluminum hydroxides are dissolved in excess 25% sodium hydroxide. The resulting basic solution is extracted twice with ether, and the combined extracts are then washed with 10% HC1. Neutralization of the acidic wash with 10% sodium hydroxide precipitates product 6, which is extracted back into fresh ether. The ether solution is dried over anhydrous sodium sulfate and stripped. The crude product is purified by repeated sublimation on a steam bath under vacuum.
  • Example 4 Preparation of polymeric heterodimondoids coupled by double bonds between carbons on diamond lattice positions This example describes an exemplary method that may be used to prepare polymeric heterodimondoids coupled by double bonds between carbon atoms positioned on diamond lattice positions of adjacent heterodiamondoids.
  • many different configuration of polymeric heterodiamondoids may be prepared, including cyclic, linear, and zig-zag polmers, depending on the positions of the carbon atoms within the diamondoid itself. It will be understood by those skilled in the art that there may be a substantially unlimited number of configurations that may be prepared using the methodology of the present embodiments, but a specific oxidation reaction will be described next, and the coupling reaction is described in Example 9.
  • Hetero-diamondoidone (keto-heterodiamondoid) is prepared by adding 10 mmoles of hetero-diamondoid to 100 mL of 96% sulfuric acid. The reaction mixture is then heated for about five hours at about 75 °C with vigorous stirring. Stirring is continued at room temperature for about one additional hour. The black reaction mixture is poured over ice and steam distilled. The steam distillate is extracted with ether, and the combined ether extracts are washed with water and dried over MgSO 4 . Ether is evaporated to yield a crude product mixture.
  • the intermediate chlorides are converted to a mixture of the corresponding alcohols and ketones by heating them to around 100 °C in solution of sodium bicarbonate in DMSO for several hours.
  • the product mixture is partitioned between hexane and water and the hexane layer evaporated to yield the product mixture.
  • Conversion of the remaining alcohols to ketones is accomplished by refluxing with a 0.15 mol solution of PCC while stirring for about 2 hours.
  • the ketones are isolated by adding a large excess of diethyl ether to the cooled mixture and washing all solids with additional ether.
  • the ether solution is passed through a short pad of Florisil and the ether evaporated to yield the ketone products with different positional or stereo isomers which may be separated and used for subsequent coupling reactions.
  • High selectivity for ketone introduction adjacent to double bonds can also be accomplished by selective bromination as shown following: to a solution of 3 mmol of the double bond coupled heterodiamondoid in 40 mL of CH C1 2 is added 6.6 mmol (1.175 g) of N-bromosuccinimide (NBS). The reaction mixture is refluxed and stirred for about 12 hours. The reaction mixture is diluted with CH 2 C1 2 and washed twice with water and a saturated Na 2 S 2 O 3 solution. The organic layer is dried over MgSO 4 and evaporated. The yield of the brominated products is about 90%. Conversion of this intermediate to ketone products is accomplished using the same procedure above.
  • Example 6 Preparation ofD ⁇ ketones of Heterodiamondoids
  • Diketones of heterodiamondoids can be produced by more vigorous oxidation than the above examples (Examples 4 and 5) using strong oxidizing agents such as H 2 SO 4 or CrO 3 /Ac 2 0 but are preferably produced by a sequence of oxidations.
  • the monoketones are generally treated with a solution of CrO 3 in acetic anhydride at near room temperature for about 2 days.
  • the reaction is quenched with dilute aqueous caustic (NaOH), and the product isolated by extraction with diethyl ether.
  • the product diketones are then separated and used for coupling reactions.
  • Example 7 Preparation of Adjacent Ketones on the Same Heterodiamondoid Face
  • a particularly useful oxidation procedure to produce adjacent ketones on the same diamondoid face is to selectively oxidize an intermediate ketone with SeO /H 2 O 2 to a lactone, then rearrange the lactone to an hydroxyketone with strong acid and oxidize that hydroxyketone to the desired diketone.
  • a monoketone heterodiamondoid is treated at elevated temperature with a 1.5 molar excess of SeO 2 in 30% H 2 O 2 at around 60 °C for several hours.
  • the mixed lactone products are isolated by dilution of the reaction solution with water, extraction with hexane and removal of the hexane by evaporation.
  • the lactones are hydrolyzed and rearranged by heating with 50% H 2 SO 4 . Again the products are isolated as above and further converted to a mixture of positional diketone isomers which are isolated and used for further coupling reactions.
  • Example 8 Preparation of Mixed Keto-Heterodiamondoids
  • a composition containing a mixture of heterodiamondoids (heterotetramantanes, heteropentamantanes, and the like) is oxidized to produce a mixture of ketones by treatment with 96% H 2 SO 4 at about 75 °C for about 10 hours or by treating with CrO /Ac 2 O at near room temperature for about one day.
  • the TiCl 3 /THF mixture is cooled to about 0°C, and the desired amount (generally 15 to 50 mmol) of LiAlH 4 is added in small portions to keep the vigorous reaction (H evolution) under control. After the addition, the reaction mixture is stirred at 0°C for about 0.5 hour. If hydrogenation as a side reaction is to be minimized, the black suspension of (M) is refluxed for an additional hour.
  • the coupling reaction is carried out as follows: the desired amount of ketone (generally 10 to 20 mmol of ketone groups) is added to the cooled, black suspension of (M).
  • cyclic trimers are preferred in these cyclization but cyclic trimers also form in special cases. It will be understood by those skilled in the art that it is possible to produce polymeric heterodiamondoids from different keto-heterodiamondoids, their different positional isomers and stereo isomers under this coupling conditions.
  • Two dimensional sheet polymers can be formed from heterodiamondoids bearing more than 2 ketone groups. Such precursors can be formed by extended oxidations of the parent hetero diamondoids, or by sequential oxidation/couplings as described in the above examples. Cyclic tetramers are particularly useful as intermediates in the production of two dimensional sheets through additional oxidation/coupling sequences as described in the previous examples.
  • ketones In addition to polymerization using the McMurray coupling reaction other methods of forming double bonds between hetero diamondoids are useful.
  • This procedure is useful as it allows one to systematically produce mixed coupled diamondoid polymers by sequential reaction of one hetero diamondoid then another with hydrazine to form mixed azines.
  • the removal of byproducts from the coupled hetero diamondoids is also easier.
  • the following is an example of the coupling of heterodiamondoids via this route.
  • a solution of hydrazine hydrate (98%, 1.30 g, 26 mmol) in 15 mL of tert-butyl alcohol is added dropwise under nitrogen over a period of about 45 minutes to a stirred refluxing solution of a heterodiamondoidone (35 mmol) in 60 mL of tert-butyl alcohol.
  • the solution is refluxed for about an additional 12 hours and subsequently allowed to stand at ambient temperature for about 24 hours.
  • the solvent is removed to give an crystalline mass ti which is added 200 mL of water.
  • the aqueous mixture is extracted with ether (4x100 mL).
  • the combined ether extracts are washed with brine, dried (MgSO 4 ), and the azine product recrystallized.
  • hydrogen sulfide is bubbled through a solution of the above azine (41.1 mmol), and 5 mg of p-toluenesilfonic acid in 300 mL of 1:3 acetone:benzene at ambient temperature. Conversion is complete after about 12 hours.
  • thiadiazine with yields of about 90% as a yellow residue. This material is used in the subsequent step without further purification.

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Abstract

Novel heterodiamondoid-containing field emission devices (FED's) are disclosed herein. In one embodiment of the present invention, the heteroatom of the heterodiamondoid comprises an electron-donating species (such as nitrogen) as part of the cathode or electron-emitting component of the field emission device.

Description

HETERODIAMONDOID-CONTAINING FIELD EMISSION DEVICES
BACKGROUND OF THE INVENTION
Field of the Invention Embodiments of the present invention are generally directed toward novel uses of heterodiamondoids and heterodiamondoid-containing materials in field emission devices. Specifically, the heteroatoms of the heterodiamondoids of the present embodiments are electron donating species, and the field emission device (FED) contains an electron-emitting cold cathode.
State of the Art Carbon-containing materials offer a variety of potential uses in microelectronics. As an element, carbon displays a variety of different structures, some crystalline, some amorphous, and some having regions of both, but each form having a distinct and potentially useful set of properties. A review of carbon's structure-property relationships has been presented by S. Prawer in a chapter titled "The Wonderful World of Carbon," in Physics of Novel Materials (World Scientific, Singapore, 1999), pp. 205-234. Prawer suggests the two most important parameters that may be used to predict the properties of a carbon-containing material are, first, the ratio of sp2 to sp3 bonding in a material, and second, microstructure, including the crystallite size of the material, i.e. the size of its individual grains. Elemental carbon has the electronic structure ls22s22p2, where the outer shell
2s and 2p electrons have the ability to hybridize according to two different schemes. The so-called sp3 hybridization comprises four identical σ bonds arranged in a tetrahedral manner. The so-called sp -hybridization comprises three trigonal (as well as planar) σ bonds with an unhybridized p electron occupying a π orbital in a bond oriented perpendicular to the plane of the σ bonds. At the "extremes" of crystalline morphology are diamond and graphite. In diamond, the carbon atoms are tetrahedrally bonded with sp3 -hybridization. Graphite comprises planar "sheets" of sp2-hybridized atoms, where the sheets interact weakly through perpendicularly oriented π bonds. Carbon exists in other morphologies as well, including amorphous forms called "diamond-like carbon," and the highly symmetrical spherical and rod- shaped structures called "fullerenes" and "nanotubes," respectively. Diamond is an exceptional material because it scores highest (or lowest, depending on one's point of view) in a number of different categories of properties. Not only is it the hardest material known, but it has the highest thermal conductivity of any material at room temperature. It displays superb optical transparency from the infrared through the ultraviolet, has the highest refractive index of any clear material, and is an excellent electrical insulator because of its very wide bandgap. It also displays high electrical breakdown strength, and very high electron and hole mobilities. If diamond as a microelectronics material has a flaw, it would be that while diamond may be effectively doped with boron to make a p-type semiconductor, efforts to implant diamond with electron-donating elements such as phosphorus, to fabricate an n-type semiconductor, have (to the inventors' knowledge) thus far been unsuccessful. Attempts to synthesize diamond films using chemical vapor deposition (CVD) techniques date back to about the early 1980's. An outcome of these efforts was the appearance of new forms of carbon largely amorphous in nature, yet containing a high degree of sp -hybridized bonds, and thus displaying many of the characteristics of diamond. To describe such films the term "diamond-like carbon" (DLC) was coined, although this term has no precise definition in the literature. In "The Wonderful World of Carbon," Prawer teaches that since most diamond-like materials display a mixture of bonding types, the proportion of carbon atoms which are four-fold coordinated (or sp -hybridized) is a measure of the "diamond-like" content of the material. Unhybridized p electrons associated with sp2-hybridization form π bonds in these materials, where the π bonded electrons are predominantly delocalized. This gives rise to the enhanced electrical conductivity of materials with sp bonding, such as graphite. In contrast, sp -hybridization results in the extremely hard, electrically insulating and transparent characteristics of diamond. The hydrogen content of a diamond-like material will be directly related to the type of bonding it has. In diamond-like materials the bandgap gets larger as the hydrogen content increases, and hardness often decreases. Not surprisingly, the loss of hydrogen from a diamond-like carbon film results in an increase in electrical activity and the loss of other diamond-like properties as well. Nonetheless, it is generally accepted that the term "diamond-like carbon" may be used to describe two different classes of amorphous carbon films, one denoted as "a:C-H," because hydrogen acts to terminate dangling bonds on the surface of the film, and a second hydrogen-free version given the name "ta-C" because a majority of the carbon atoms are tetrahedrally coordinated with sp3- hybridization. The remaining carbons of ta-C are surface atoms that are substantially sp2-hybridized. In a:C-H, dangling bonds can relax to the sp2 (graphitic) configuration. The role hydrogen plays in a:C-H is to prevent unterminated carbon atoms from relaxing to the graphite structure. The greater the sp content the more "diamond-like" the material is in its properties such as thermal conductivity and electrical resistance. In his review article, Prawer states that tetrahedral amorphous carbon (ta-C) is a random network showing short-range ordering that is limited to one or two nearest neighbors, and no long-range ordering. There may be present random carbon networks that may comprise 3, 4, 5, and 6-membered carbon rings. Typically, the maximum sp3 content of a ta-C film is about 80 to 90 percent. Those carbon atoms that are sp2 bonded tend to group into small clusters that prevent the formation of dangling bonds. The properties of ta-C depend primarily on the fraction of atoms having the sp3, or diamond-like configuration. Unlike CND diamond, there is no hydrogen in ta-C to passivate the surface and to prevent graphite-like structures from forming. The fact that graphite regions do not appear to form is attributed to the existence of isolated sp bonding pairs and to compressive stresses that build up within the bulk of the material. The microstructure of a diamond and/or diamond-like material further determines its properties, to some degree because the microstructure influences the type of bonding content. As discussed in "Microstructure and grain boundaries of ultrananocrystalline diamond films" by D. M. Gruen, in Properties, Growth and Applications of Diamond, edited by M. H. Νazare and A. J. Νeves (Inspec, London, 2001), pp. 307-312, recently efforts have been made to synthesize diamond having crystallite sizes in the "nano" range rathe'r than the "micro" range, with the result that grain boundary chemistries may differ dramatically from those observed in the bulk. Nanocrystalline diamond films have grain sizes in the three to five nanometer range, and it has been reported that nearly 10 percent of the carbon atoms in a nanocrystalline diamond film reside in grain boundaries. In Gruen's chapter, the nanocrystalline diamond grain boundary is reported to be a high-energy, high angle twist grain boundary, where the carbon atoms are largely π-bonded. There may also be sp2 bonded dimers, and chain segments with sp3 -hybridized dangling bonds. Nanocrystalline diamond is apparently electrically conductive, and it appears that the grain boundaries are responsible for the electrical conductivity. The author states that a nanocrystalline material is essentially a new type of diamond film whose properties are largely determined by the bonding of the carbons within grain boundaries. Another allotrope of carbon known as the fullerenes (and their counterparts carbon nanotubes) has been discussed by M.S. Dresslehaus et al. in a chapter entitled "Nanotechnology and Carbon Materials," in Nanotechnology (Springer-Nerlag, New York, 1999), pp. 285-329. Though discovered relatively recently, these materials already have a potential role in microelectronics applications. Fullerenes have an even number of carbon atoms arranged in the form of a closed hollow cage, wherein carbon-carbon bonds on the surface of the cage define a polyhedral structure. The fullerene in the greatest abundance is the C60 molecule, although C70 and C80 fullerenes are also possible. Each carbon atom in the C60 fullerene is trigonally bonded with sp2-hybridization to three other carbon atoms. C60 fullerene is described by Dresslehaus as a "rolled up" graphine sheet forming a closed shell (where the term "graphine" means a single layer of crystalline graphite). Twenty of the 32 faces on the regular truncated icosahedron are hexagons, with the remaining 12 being pentagons. Every carbon atom in the C60 fullerene sits on an equivalent lattice site, although the three bonds emanating from each atom are not equivalent. The four valence electrons of each carbon atom are involved in covalent bonding, so that two of the three bonds on the pentagon perimeter are electron-poor single bonds, and one bond between two hexagons is an electron-rich double bond. A fullerene such as C60 is further stabilized by the Kekule structure of alternating single and double bonds around the hexagonal face. Dresslehaus et al. further teach that, electronically, the C60 fullerene molecule has 60 π electrons, one π electronic state for each carbon atom. Since the highest occupied molecular orbital is fully occupied and the lowest un-occupied molecular orbital is completely empty, the C60 fullerene is considered to be a semiconductor with very high resistivity. Fullerene molecules exhibit weak van der Waals cohesive interactive forces toward one another when aggregated as a solid. The following table summarizes a few of the properties of diamond, DLC (both ta-C and a:C-H), graphite, and fullerenes:
The data in the table is compiled from p. 290 of the Dresslehaus et al. reference cited above, p. 221 of the Prawer reference cited above, p. 891 a chapter by A. Erdemir et al. in "Tribology of Diamond, Diamond-Like Carbon, and Related Films," in Modern Tribology Handbook, Vol. Two, B. Bhushan, Ed. (CRC Press, Boca Raton, 2001), and p. 28 of "Deposition of Diamond-Like Superhard Materials," by W. Kulisch, (SpringerNerlag, New York, 1999). A form of carbon not discussed extensively in the literature are "diamondoids." Diamondoids are bridged-ring cycloalkanes that comprise adamantane, diamantane, triamantane, and the tetramers, pentamers, hexamers, heptamers, octamers, nonamers, decamers, etc., of adamantane (tricyclo[3.3.1.13,7] decane), adamantane having the stoichiometric formula Cι0Hι6, in which various adamantane units are face-fused to form larger structures. These adamantane units are essentially subunits of diamondoids. The compounds have a "diamondoid" topology in that their carbon atom arrangements are superimposable on a fragment of an FCC (face centered cubic) diamond lattice. Diamondoids are highly unusual forms of carbon because while they are hydrocarbons, with molecular sizes ranging in general from about 0.2 to 20 nm (averaged in various directions), they simultaneously display the electronic properties of an ultrananocrystalline diamond. As hydrocarbons they can self- assemble into a van der Waals solid, possibly in a repeating array with each diamondoid assembling in a specific orientation. The solid results from cohesive dispersive forces between adjacent C-Hx groups, the forces more commonly seen in normal alkanes. In diamond nanocrystallites the carbon atoms are entirely sp3 -hybridized, but because of the small size of the diamondoids, only a small fraction of the carbon atoms are bonded exclusively to other carbon atoms. The majority have at least one hydrogen nearest neighbor. Thus, the majority of the carbon atoms of a diamondoid occupy surface sites (or near surface sites), giving rise to electronic states that are significantly different energetically from bulk energy states. Accordingly, diamondoids are expected to have unusual electronic properties. To the inventors' knowledge, adamantane, substituted adamantanes, and perhaps diamantane are the only readily available diamondoids. Some diamantanes, substituted diamantanes, triamantanes, and substituted triamantanes have been studied, and only a single tetramantane has been synthesized. The remaining diamondoids are provided for the first time by the inventors, and are described in their co-pending U.S. Provisional Patent Applications Nos. 60/262,842, filed January 19, 2001; 60/300,148, filed June 21, 2001; 60/307,063, filed July 20, 2001; 60/312,563, filed August 15, 2001; 60/317,546, filed September 5, 2001; 60/323,883, filed September 20, 2001; 60/334,929, filed December 4, 2001; and 60/334,938, filed December 4, 2001, incorporated herein in their entirety by reference. Applicants further incorporate herein by reference, in their entirety, the non-provisional applications sharing these titles which were filed on December 12, 2001. The diamondoids that are the subject of these co-pending applications have not been made available for study in the past, and to the inventors' knowledge they have never been used before in as an elecron-emitting cathode in a field emission device.
SUMMARY OF THE INVENTION Embodiments of the present invention are generally directed toward novel uses of heterodiamondoids and heterodiamondoid-containing materials in field emission devices. Specifically, the heteroatoms of the heterodiamondoids of the present embodiments are electron donating species, and the field emission device (FED) contains an electron-emitting cathode. The term "heterodiamondoid" as used herein refers to a diamondoid that contains a heteroatom typically substitutionally positioned on a lattice site of the diamond crystal structure. A heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic. "Substitutionally positioned" means that the heteroatom has replaced a carbon host atom in the diamond lattice. Exemplary methods for fabricating w-type materials from heterodiamondoid compounds include CVD techniques, polymerization techniques, crystallization of the heterodiamondoids by themselves, or crystallization of the heterodiamondoids along with with other materials, and use of diamondoids and/or heterodiamondoids at the molecular level. According to embodiments of the present invention, a heterodiamondoid or heterodiamondoid-containing material is utilized as a cathode filament in a field emission device suitable for use, among other places, in flat panel displays. The unique properties of a heteroatom-containing diamondoid make this possible. These properties include an electron-donating species to contribute electrons to the conduction band of the filament material, the negative electron affinity of a hydrogenated diamond surface, in conjunction with the small size and predictable structure of a typical heterodiamondoid compound. The heterodiamondoid may be derivatized or underivatized, and may be derived from a lower diamondoid (adamantane, diamantane, and triamantane), a higher diamondoid (tetramantane and higher), and/or combinations thereof. The filament material (wherein the term
"filament" is used interchangeably with the term "cathode") may be in the form of a film or a fiber. The heterodiamondoid-containing material is selected from the group consisting of a heterodiamondoid-containing polymer, a heterodiamondoid- > containing CND film, and a heterodiamondoid-containing molecular crystal. In the present embodiments, the electron affinity of the cathode is less than about 3 eN, and the electron affinity may be negative.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an overview of the embodiments of the present invention, showing the steps of isolating diamondoids from petroleum, synthesizing heterodiamondoids, preparing π-type materials therefrom, and then fabricating a field emission device (FED) based on the heterodiamondoid-containing material; FIG. 2 shows an exemplary process flow for isolating diamondoids from petroleum; FIG. 3 illustrates the relationship of a diamondoid to the diamond crystal lattice, and enumerates by stoichiometric formula many of the diamondoids available; FIGS. 4A-B illustrate exemplary positions of the electron-donating heteroatom on a carbon atom lattice site of two exemplary diamondoids; FIGS. 5A-B illustrate exemplary pathways for synthetically producing a nitrogen-containing heterodiamondoid; FIG. 6 illustrates an exemplary processing reactor in which an n-type heterodiamondoid material may be made using chemical vapor deposition (CND) techniques; FIGS. 7A-C illustrate an exemplary process whereby a heterodiamondoid may be used to introduce dopant impurity atoms into a growing diamond film; FIG. 8 is an exemplary reaction scheme for the synthesis of a polymer from heterodiamondoids; FIGS. 9A-Ν show exemplary linking groups that may be electrically conducting, and that may be used to link heterodiamondoids to produce π-type materials; FIG. 10 illustrates an exemplary -type material fabricated from heterodiamondoids linked by polyaniline oligomers; FIG. 11 shows how [1(2,3)4] pentamantane packs to form a molecular crystal; FIG. 12 shows how individual heterodiamondoids may be coupled to form an n-type heterodiamondoid cluster at the molecular level, where such a cluster may contain j^-type heterodiamondoids as well; and FIG. 13 is a schematic, cross-sectional diagram of an exemplary field emission device, wherein a single diamondoid, or diamondoid-containing material may be used as the cathode filament component of the device. DETAILED DESCRIPTION OF THE INVENTION The present disclosure will be organized as follows: first, a definition of diamondoids and heterodiamondoids will be given, followed by a description of how diamondoids may be isolated from petroleum feedstocks. Next, exemplary methods for synthesizing electron-donating heterodiamondoids will be given, followed by how 72 -type heterodiamondoid materials may be prepared from the electron-donating heterodiamondoids. After this the properties of n-type diamond will be discussed briefly, and how those properties are contemplated to relate to heterodiamondoid- containing field emission devices. The present disclosure will conclude with examples of the actual synthesis of some nitrogen-containing heterodiamondoids.
Definition of heterodiamondoids The term "diamondoid" refers to substituted and unsubstituted caged compounds of the adamantane series. The "lower diamondoids" are defined to be adamantane, diamantane, and triamantane, including substituted and unsubstituted compounds thereof. "Higher diamondoids" are defined to include tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, undecamantane, and the like, including all isomers and stereoisomers thereof. The compounds have a "diamondoid" topology, which means their carbon atom arrangement is superimposable on a fragment of an FCC diamond lattice. Substituted diamondoids comprise from 1 to 10 and preferably 1 to 4 independently- selected alkyl substituents. Adamantane chemistry has been reviewed by Fort, Jr. et al. in "Adamantane: Consequences of the Diamondoid Structure," Chem. Rev. vol. 64, pp. 277-300 (1964). Adamantane is the smallest member of the diamondoid series and may be thought of as a single cage crystalline subunit. Diamantane contains two subunits, triamantane three, tetramantane four, and so on. While there is only one isomeric form of adamantane, diamantane, and triamantane, there are four different isomers of tetramantane (two of which represent an enantiomeric pair), i.e., four different possible ways of arranging the four adamantane subunits. The number of possible isomers increases non-linearly with each higher member of the diamondoid series, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, etc. Adamantane, which is commercially available, has been studied extensively. The studies have been directed toward a number of areas, such as thermodynamic stability, functionalization, and the properties of adamantane-containing materials. For instance, the following patents discuss materials comprising adamantane subunits: U.S. Patent No. 3,457,318 teaches the preparation of polymers from alkenyl adamantanes; U.S. Patent No. 3,832,332 teaches a polyamide polymer forms from alkyladamantane diamine; U.S. Patent No. 5,017,734 discusses the formation of thermally stable resins from adamantane derivatives; and U.S. Patent No. 6,235,851 reports the synthesis and polymerization of a variety of adamantane derivatives. In contrast, the diamondoids tetramantane and higher have received comparatively little attention in the scientific literature. McKervey et al. have reported the synthesis of anti- tetramantane in low yields using a laborious, multistep process in "Synthetic Approaches to Large Diamondoid Hydrocarbons,"
Tetrahedron, vol. 36, pp. 971-992 (1980). To the inventors' knowledge, this is the only higher diamondoid that has been synthesized to date. Lin et al. have suggested the existence of, but did not isolate, tetramantane, pentamantane, and hexamantane in deep petroleum reservoirs in light of mass spectroscopic studies, reported in "Natural Occurrence of Tetramantane (C22H28), Pentamantane (C26H32) and
Hexamantane (C30H36) in a Deep Petroleum Reservoir," Fuel, vol. 74(10), pp. 1512- 1521 (1995). The possible presence of tetramantane and pentamantane in pot material after a distillation of a diamondoid-containing feedstock has been discussed by Chen et al. in U.S. Patent No. 5,414, 189. The four tetramantane structures are isO-tetramantane [1(2)3], anti- tetramantane [121] and two enantiomers of sfew-tetramantane [123], with the bracketed nomenclature for these diamondoids in accordance with a convention established by Balaban et al. in "Systematic Classification and Nomenclature of Diamond Hydrocarbons-I," Tetrahedron vol. 34, pp. 3599-3606 (1978). All four tetramantanes have the formula C2 H28 (molecular weight 292). There are ten possible pentamantanes, nine having the molecular formula C26H 2 (molecular weight 344) and among these nine, there are three pairs of enantiomers represented generally by [12(1)3], [1234], [1213] with the nine enantiomeric pentamantanes represented by [12(3)4], [1(2,3)4], [1212]. There also exists a pentamantane [1231] represented by the molecular formula C 5H3o (molecular weight 330). Hexamantanes exist in thirty nine possible structures with twenty eight having the molecular fonnula C 0H36 (molecular weight 396) and of these, six are symmetrical; ten hexamantanes have the molecular formula C 9H3 (molecular weight 382) and the remaining hexamantane [12312] has the molecular formula C26H 0 (molecular weight 342). Heptamantanes are postulated to exist in 160 possible structures with 85 having the molecular fonnula C34H40 (molecular weight 448) and of these, seven are achiral, having no enantiomers. Of the remaining heptamantanes 67 have the molecular formula C33H38 (molecular weight 434), six have the molecular formula C32H36 (molecular weight 420) and the remaining two have the molecular formula C30H34 (molecular weight 394). Octamantanes possess eight of the adamantane subunits and exist with five different molecular weights. Among the octamantanes, 18 have the molecular formula C34H38 (molecular weight 446). Octamantanes also have the molecular formula C38H 4 (molecular weight 500); C37H42 (molecular weight 486); C36H40 (molecular weight 472), and C33H36 (molecular weight 432). Nonamantanes exist within six families of different molecular weights having the following molecular formulas: C42H48 (molecular weight 552), C4ιH46 (molecular weight 538), C40H44 (molecular weight 524, C38H42 (molecular weight 498), C37H40 (molecular weight 484) and C34H36 (molecular weight 444). Decamantane exists within families of seven different molecular weights. Among the decamantanes, there is a single decamantane having the molecular formula C35H36 (molecular weight 456) which is structurally compact in relation to the other decamantanes. The other decamantane families have the molecular formulas: C46H52 (molecular weight 604); C45H50 (molecular weight 590); C44H 8 (molecular weight 576); C42H46 (molecular weight 550); C4ιH44 (molecular weight 536); and C38H40 (molecular weight 496). Undecamantane exists within families of eight different molecular weights.
Among the undecamantanes there are two undecamantanes having the molecular formula C39H40 (molecular weight 508) which are structurally compact in relation to the other undecamantanes. The other undecamantane families have the molecular formulas C4ιH42 (molecular weight 534); C4 H44 (molecular weight 548); C45H48 (molecular weight 588); C46H50 (molecular weight 602); C48H5 (molecular weight 628); C4 H54 (molecular weight 642); and C5oH56 (molecular weight 656). The term "heterodiamondoid" as used herein refers to a diamondoid that contains a heteroatom typically substitutionally positioned on a lattice site of the diamond crystal structure. A heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic. "Substitutionally positioned" means that the heteroatom has replaced a carbon host atom in the diamond lattice. Although most heteroatoms are substitutionally positioned, they may in some cases be found in interstitial sites as well. As with diamondoids, a heterodiamondoid may be functionalized or derivatized; such compounds may be referred to as substituted heterodiamondoids. In the present disclosure, an »-type diamondoid typically refers to an rø-type heterodiamondoid, but in some cases the rc-type material may comprise diamondoids with no heteroatom. Although heteroadamantane and heterodiamantane compounds have been reported in the literature, to the inventors' knowledge, no hetero triamantane or higher compounds have been previously synthesized, and there is no reported case of the use of a heterodiamondoid, including heteroadamantane or heterodiamantane compounds as «-type materials as part of a field emission device, such as the cathode of the device. The inventors contemplate the use of 1) heteroadamantane and heterodiamantane, or 2) heterotriamantane, or 3) heterotetramantane and above as potential materials for the cathodes of field emission devices; however, n-type materials comprising the heterodiamondoids from tetramantane and above are expected to have advantages due to the higher carbon-to-hydrogen ratios, (where more carbons are in quaternary positions where they are bonded only to other carbons). There may be mechanical advantages as well. FIG. 2 shows a process flow illustrated in schematic form, wherein diamondoids may be extracted from petroleum feedstocks, and FIG. 3 enumerates the various diamondoid isomers that are available according to embodiments of the present invention.
Isolation of diamondoids from petroleum feedstocks Feedstocks that contain recoverable amounts of higher diamondoids include, for example, natural gas condensates and refinery streams resulting from cracking, distillation, coking processes, and the like. Particularly preferred feedstocks originate from the Norphlet Formation in the Gulf of Mexico and the LeDuc Formation in Canada. These feedstocks contain large proportions of lower diamondoids (often as much as about two thirds) and lower but significant amounts of higher diamondoids (often as much as about 0.3 to 0.5 percent by weight). The processing of such feedstocks to remove non-diamondoids and to separate higher and lower diamondoids (if desired) can be carried out using, by way of example only, size separation techniques such as membranes, molecular sieves, etc., evaporation and thermal separators either under normal or reduced pressures, extractors, electrostatic separators, crystallization, chromatography, well head separators, and the like. A preferred separation method typically includes distillation of the feedstock. This can remove low-boiling, non-diamondoid components. It can also remove or separate out lower and higher diamondoid components having a boiling point less than that of the higher diamondoid(s) selected for isolation. In either instance, the lower cuts will be enriched in lower diamondoids and low boiling point non- diamondoid materials. Distillation can be operated to provide several cuts in the temperature range of interest to provide the initial isolation of the identified higher diamondoid. The cuts, which are enriched in higher diamondoids or the diamondoid of interest, are retained and may require further purification. Other methods for the removal of contaminants and further purification of an enriched diamondoid fraction can additionally include the following nonlimiting examples: size separation techniques, evaporation either under normal or reduced pressure, sublimation, crystallization, chromatography, well head separators, flash distillation, fixed and fluid bed reactors, reduced pressure, and the like. The removal of non-diamondoids may also include a thermal treatment step either prior or subsequent to distillation. The thermal treatment step may include a hydrotreating step, a hydrocracking step, a hydroprocessing step, or a pyrolysis step. Thermal treatment is an effective method to remove hydrocarbonaceous, non- diamondoid components from the feedstock, and one embodiment of it, pyrolysis, is effected by heating the feedstock under vacuum conditions, or in an inert atmosphere, to a temperature of at least about 390°C, and most preferably to a temperature in the range of about 410 to 450°C. Pyrolysis is continued for a sufficient length of time, and at a sufficiently high temperature, to thermally degrade at least about 10 percent by weight of the non-diamondoid components that were in the feed material prior to pyrolysis. More preferably at least about 50 percent by weight, and even more preferably at least 90 percent by weight of the non- diamondoids are thermally degraded. While pyrolysis is preferred in one embodiment, it is not always necessary to facilitate the recovery, isolation or purification of diamondoids. Other separation methods may allow for the concentration of diamondoids to be sufficiently high given certain feedstocks such that direct purification methods such as chromatography including preparative gas chromatography and high performance liquid chromatography, crystallization, fractional sublimation may be used to isolate diamondoids. Even after distillation or pyroly sis/distillation, further purification of the material may be desired to provide selected diamondoids for use in the compositions employed in this invention. Such purification techniques include chromatography, crystallization, thermal diffusion techniques, zone refining, progressive recrystallization, size separation, and the like. For instance, in one process, the recovered feedstock is subjected to the following additional procedures: 1) gravity column cliromatography using silver nitrate impregnated silica gel; 2) two-column preparative capillary gas chromatography to isolate diamondoids; and/or 3) crystallization to provide crystals of the highly concentrated diamondoids. An alternative process is to use single or multiple column liquid chromatography, including high performance liquid chromatography, to isolate the diamondoids of interest. As above, multiple columns with different selectivities may be used. Further processing using these methods allow for more refined separations which can lead to a substantially pure component. Detailed methods for processing feedstocks to obtain higher diamondoid compositions are set forth in U.S. Provisional Patent Application No. 60/262,842 filed January 19, 2001; U.S. Provisional Patent Application No. 60/300,148 filed June 21, 2001; and U.S. Provisional Patent Application No. 60/307,063 filed July 20, 2001, and a co-pending application titled "Processes for concentrating higher diamondoids," by B. Carlson et al., assigned to the assignee of the present application. These applications are herein incorporated by reference in their entirety. FIG. 2 shows a process flow illustrated in schematic form, wherein diamondoids may be extracted from petroleum feedstocks, and FIG. 3 enumerates the various diamondoid isomers that are available from embodiments of the present invention.
Synthesis of heterodiamondoids The term "heterodiamondoid" as used herein refers to a diamondoid that contains a heteroatom typically substitionally positioned on a lattice site of the diamond crystal structure. A heteroatom is an atom other than carbon, and according to present embodiments may be nitrogen, phosphorus, boron, aluminium, lithium, and arsenic. "Substitutionally positioned" means that the heteroatom has replaced a carbon host atom in the diamond lattice. Although most heteroatoms are substitutionally positioned, they may in some cases be found in interstitial sites as well. FIG. 4 illustrates exemplary heterodiamondoids, indicating the types of carbon positions where a heteroatom may be substitutionally positioned. These positions are labelled C-2 and C-3 in the exemplary diamondoid of FIG. 4. The term "diamondoid" will herein be used in a general sense to include diamondoids both with and without heteroatom substitutions. As disclosed above, the heteroatom may be an electron donating element such as N, P, or As, or a hole donating element such as B or Al. Emphasis in this disclosure will be placed on the nitrogen-containing heterodiamondoid, since it is the properties of the electron-donating nitrogen atom that are the focus of the present field emission devices. An exemplary synthesis of such heterodiamondoids will be discussed next. Although some heteroadamantane and heterodiamantane compounds have been synthesized in the past, and this may suggest a starting point for the synthesis of heterodiamondoids having more than two or three fused adamantane subunits, it will be appreciated by those skilled in the art that the complexity of the individual reactions and overall synthetic pathways increase as the number of adamantane subunits increases. For example, it may be necessary to employ protecting groups, or it may become more difficult to solubilize the reactants, or the reaction conditions may be vastly different from those that would have been used for the analagous reaction with adamantane. Nevertheless, it can be advantageous to discuss the chemistry underlying heterodiamondoid synthesis using adamantane or diamantane as a substrate because to the inventors' knowledge these are the only systems for which data has been available, prior to the present application. Nitrogen hetero-adamantane compounds have been synthesized in the past.
For example, in an article by T. Sasaki et al., "Synthesis of adamantane derivatives. 39. Synthesis and acidolysis of 2-azidoadamantanes. A facile route to 4- azahomoadamant-4-enes," Heterocycles, Vol. 7, No. 1, p. 315 (1977). These authors reported a synthesis of 1-azidoadamantane and 3-hydroxy-4-azahomoadamantane from 1 -hydroxyadamantane. The procedure consisted of a substitution of a hydroxyl group with an azide function via the formation of a carbocation, followed by acidolysis of the azide product. In a related synthetic pathway, Sasaki et al. were able to subject an adamantanone to the conditions of a Schmidt reaction, producing a 4-keto-3- azahomoadamantane as a rearranged product. For details pertaining to the Schmidt reaction, see T. Sasaki et al., "Synthesis of Adamantane Derivatives. XII. The Schmidt Reaction of Adamantane-2-one," J. Org. Chem., Vol. 35, No. 12, p. 4109 (1970). Alternatively, an l-hydroxy-2-azaadamantane may be synthesized from 1,3- dibromoadamantane, as reported by A. Gagneux et al. in "1 -Substituted 2- heteroadamantanes," Tetrahedron Letters No. 17, pp. 1365-1368 (1969). This was a multiple-step process, wherein first the di-bromo starting material was heated to a methyl ketone, which subsequently underwent ozonization to a diketone. The diketone was heated with four equivalents of hydroxylamine to produce a 1:1 mixture of cis and trans-dioximes; this mixture was hydrogenated to the compound l-amino-2-azaadamantane dihydrochloride. Finally, nitrous acid transformed the dihydrochloride to the hetero-adamantane l-hydroxy-2-azadamantane. Alternatively, a 2-azaadamantane compound may be synthesized from a bicyclo[3.3.1]nonane-3,7-dione, as reported by J.G. Henkel and W.C. Faith, in "Neighboring group effects in the β-halo amines. Synthesis and solvolytic reactivity of the β«tz'-4-substituted 2-azaadamantyl system," in J Org. Chem. Vol. 46, No. 24, pp. 4953-4959 (1981). The dione may be converted by reductive amination
(although the use of ammonium acetate and sodium cyanoborohydride produced better yields) to an intermediate, which may be converted to another intermediate using thionyl choloride. Dehalogenation of this second intermediate to 2- azaadamantane was accomplished in good yield using LiAlH4 in DME. A synthetic pathway that is related in principal to one used in the present invention was reported by S. Eguchi et al. in "A novel route to the 2-aza-adamantyl system via photochemical ring contraction of epoxy 4-azahomoadamantanes," J. Chem. Soc. Chem. Commun., p. 1147 (1984). In this approach, a 2- hydroxyadamantane was reacted with a NaN3 based reagent system to form the azahomoadamantane, with was then oxidized by w-chloroperbenzoid acid (m-
CPBA) to give an epoxy 4-azahomoadamantane. The epoxy was then irradiated in a photochemical ring contraction reaction to yield the N-acyl-2-aza-adamantane. An exemplary reaction pathway for synthesizing a nitrogen-containing hetero tso-tetramantane is illustrated in FIG. 5 A. It will be known to those of ordinary skill in the art that the reactions conditions of the pathway depicted in FIG. 5 A will be substantially different from those of Eguchi due to the differences in size, solubility, and reactivities of tetramantane in relation to adamantane. A second pathway available for synthesizing nitrogen containing heterodiamondoids is illustrated in FIG. 5B. In another embodiment of the present invention, a phosphorus-containing heterodiamondoid may be synthesized by adapting the pathway outlined by J. J. Meeuwissen et. al in "Synthesis of 1-phosphaadamantane," Tetrahedron Nol. 39, No. 24, pp. 4225-4228 (1983). It is contemplated that such a pathway may be able to synthesize heterodiamondoids that contain both nitrogen and phosphorus atoms substitutionally positioned in the diamondoid structure, with the advantages of having two different types of electron-donating heteroatoms in the same structure. After preparing a heterodiamondoid from a diamondoid having no impurity atoms contained therein, the resulting heterodiamondoid may be functionalized to generate an electron-donating material according to embodiments of the present invention. Alternatively, the diamondoid (having no impurity atoms) may be functionalized first, and then converted to the heteroatom form. Further information on the synthesis of heterodiamondoids is provided in a
U.S. Patent Application titled "Heterodiamondoids," Serial Number 10/622,130, filed July 16, 2003, incorporated herein by reference in its entirety.
Preparation of rø-τype heterodiamondoid materials An overview of exemplary methods for fabricating n-type materials from heterodiamondoid molecules was shown in FIG. 1. These methods included CND techniques, polymerization techniques, crystallization of the heterodiamondoids by themselves, or crystallization of the heterodiamondoids along with with other materials, and use of diamondoids and/or heterodiamondoids at the molecular level. The term "materials preparation" as used herein refers to processes that take the heterodiamondoids after they have been synthesized from diamondoid feedstocks, and fabricates them into π-type diamondoid-containing materials. In a first embodiment, heterodiamondoids are injected into a reactor carrying out a conventional CND process such that the heterodiamondoids are added to and become a part of an extended diamond structure, and the heteroatom, being substitutionally positioned on a diamond lattice site, behaves like a dopant in conventionally produced doped diamond. In a second embodiment, the heterodiamondoids may be derivatized (or functionalized) with functional groups capable of undergoing a polymerization reaction, and in one variation, the functional groups linking two adjacent heterodiamondoids are electrically semiconducting. In a third embodiment, the n-type material comprises only heterodiamondoids in a bulk heterodiamondoid crystal, wherein the individual heterodiamondoids in the crystal are held together by Nan der waals (London) forces. Finally, in a fourth embodiment, a single heterodiamondoid may be used as part of the cathode of a field emission device. In the first embodiment, n-type diamondoid materials are fabricated using chemical vapor deposition (CND) techniques. Heterodiamondoids may be employed as carbon precursors and as self-contained dopant sources already sp3- hybridized in a diamond lattice, using conventional CND techniques. In a novel approach, the use of the heterodiamondoids may be used to nucleate a diamond film using conventional CND techniques, where such conventional techniques include thermal CND, laser CND, plasma-enhanced or plasma-assisted CND, electron beam CND, and the like. Conventional methods of synthesizing diamond by plasma enhanced chemical vapor deposition (PECND) techniques are well known in the art, and date back to around the early 1980's. Although it is not necessary to discuss the specifics of these methods as they relate to the present invention, one point in particular should be made since it is relevant to the role hydrogen plays in the synthesis of diamond by "conventional" plasma-CND techniques. In one method of synthesizing diamond films discussed by A. Erdemir et al. in "Tribology of Diamond, Diamond-Like Carbon, and Related Films," in Modern Tribology Handbook, Nol. Two, B. Bhushan, Ed. (CRC Press, Boca Raton, 2001) pp. 871-908, a modified microwave CND reactor is used to deposit a nanocrystalline diamond film using a C60 fullerene, or methane, gas carbon precursor. To introduce the C60 fullerene precursor into the reactor, a device called a "quartz transpirator" is attached to the reactor, wherein this device essentially heats a fullerene-rich soot to temperatures between about 550 and 600°C to sublime the C60 fullerene into the gas phase. It is contemplated that a similar device may be used to sublime heterodiamondoids into the gas phase such that they may be introduced to a CND reactor. An exemplary reactor is shown in generally at 600 in FIG. 6. A reactor 600 comprises reactor walls 601 enclosing a process space 602. A gas inlet tube 603 is used to introduce process gas into the process space 602, the process gas comprising methane, hydrogen, and optionally an inert gas such as argon. A diamondoid subliming or volatilizing device 604, similar to the quartz transpirator discussed above, may be used to volatilize and inject a diamondoid containing gas into the reactor 600. The volatilizer 604 may include a means for introducing a carrier gas such as hydrogen, nitrogen, argon, or an inert gas such as a noble gas other than argon, and it may contain other carbon precursor gases such as methane, ethane, or ethylene. Consistent with conventional CND reactors, the reactor 600 may have exhaust outlets 605 for removing process gases from the process space 602; an energy source for coupling energy into process space 602 (and striking a plasma from) process gases contained within process space 602; a filament 607 for converting molecular hydrogen to monoatomic hydrogen; a susceptor 608 onto which a diamondoid containing film 609 is grown; a means 610 for rotating the susceptor 608 for enhancing the sp3 -hybridized uniformity of the diamondoid- containing film 609; and a control system 611 for regulating and controlling the flow of gases through inlet 603; the amount of power coupled from source 606 into the processing space 602; the amount of diamondoids injected into the processing space 602; the amount of process gases exhausted through exhaust ports 405; the atomization of hydrogen from filament 607; and the means 610 for rotating the susceptor 608. In an exemplary embodiment, the plasma energy source 606 comprises an induction coil such that power is coupled into process gases within processing space 602 to create a plasma 612. A heterodiamondoid precursor may be injected into reactor 600 according to embodiments of the present invention through the volatilizer 604, which serves to volatilize the diamondoids. A carrier gas such as methane or argon may be used to facilitate transfer of the diamondoids entrained in the carrier gas into the process space 602. The injection of such heterodiamondoids provides a method whereby impurity atoms may be inserted into a diamond film without having to resort to crystal damaging techniques such as ion implantation. Alternatively, the heterodiamondoids may be introduced to the reactor simply by placing them on the substrate onto which the film will be deposited, prior to inserting the substrate into the reactor. It is contemplated in some embodiments that the injected methane gas provides the majority of the carbon material present in a CND created film, with the heterodiamondoid portion of the input gas influencing the rate of growth, crystallographic orientation, and perhaps grain structure, but more importantly, the heterodiamondoid portion of the input gas supplies the heteroatom impurity that will eventually function as the electron donating species in the n-type diamond or diamond-like film. This process is illustrated schematically in FIGS. 7A-7C. Referring to FIG. 7A, a substrate 700 is positioned within the CND reactor 600, and a conventional CND diamond film 701 is grown on the substrate 700. This diamond film 701 comprises tetrahedrally bonded carbon atoms, where a carbon atom is represented by the intersection of two lines in FIG. 7A-C, such as depicted by reference numeral 702, and a hydrogen terminated surface represented by the end of a line, as shown by reference numeral 703. The hydrogen passivated surface 703 of the diamond film 701 is very important. Hydrogen participates in the synthesis of diamond by PECND techniques by stabilizing the sp3 bond character of the growing diamond surface. As discussed in the reference cited above, A. Erdemir et al. teach that hydrogen also controls the size of the initial nuclei, dissolution of carbon and generation of condensable carbon radicals in the gas phase, abstraction of hydrogen from hydrocarbons attached to the surface of the growing diamond film, production of vacant sites where sp3 bonded carbon precursors may be inserted. Hydrogen etches most of the double or sp2 bonded carbon from the surface of the growing diamond film, and thus hinders the formation of graphitic and/or amorphous carbon. Hydrogen also etches away smaller diamond grains and suppresses nucleation. Consequently, CND grown diamond films with sufficient hydrogen present leads to diamond coatings having primarily large grains with highly faceted surfaces. Referring again to FIG. 7 A, a heterodiamondoid 704 is injected in the gas phase into the CND reactor via the volatilizing device 604 described above.
Schematically, the heterodiamondoid 704 has tetrahedrally bonded carbon atoms at the intersections of lines 702, as well as a hydrogen passivated surface at the end of the lines 703, as before. The heterodiamondoid 704 also has a heteroatom 705 substitutionally positioned within its lattice structure, and the heteroatom may be an electron donor or acceptor. During the deposition process, the heterodiamondoid 704 is deposited on the surface of the CND diamond film 701, as shown in FIG. 7B. The carbon atoms of the heterodiamondoid 704 become tetrahedrally coordinated with (bonded to) the carbon atoms of the film 701 to produce a continuous diamond lattice structure across the newly created interface of the heterodiamondoid 704 and the diamond film 701. The result is a diamond film 707 having an impurity atom (which may be an electron donor or acceptor) substitutionally positioned on a lattice site position within the diamond crystal structure, as shown in FIG. 7C. Since the heterodiamondoid has been incorporated into the growing diamond film, so has its heteroatom become incorporated into the growing film, and the heteroatom has retained its sp -hybridization characteristics through the deposition process. Advantages of the present embodiment include the insertion of an impurity atom into the diamond lattice without having to resort to crystal damaging implantation techniques. The weight of heterodiamondoids and substituted heterodiamondoids, as a function of the total weight of the CND film (where the weight of the heterodiamondoid functional groups are included in the heterodiamondoid portion), may in one embodiment range from about 1 part per million (ppm) to 10 percent by weight. In another embodiment, the content of heterodiamondoids and substituted heterodiamondoids is about 10 ppm to 1 percent by weight. In another embodiment, the proportion of heterodiamondoids and substituted heterodiamondoids in the CND film relative to the total weight of the film is about 100 ppm to 0.01 percent by weight. In an alternative embodiment, heterodiamondoids may be assembled into n- type materials by polymerization. For this to occur, it is necessary to derivatize (or functionalize) the heterodiamondoids prior to polymerization, and methods of forming diamondoid derivatives, and techniques for polymerizing derivatized diamondoids, are discussed in U.S. patent application Serial Number 10/046,486, entitled "Polymerizable Higher Diamondoid Derivatives," by Shenggao Liu, Jeremy E. Dahl, and Robert M. Carlson, filed January 16, 2002, and incorporated herein by reference in its entirety. To fabricate a polymeric film containing heterodiamondoid constituents, either as part of the main polymeric chain, or as side groups or branches off of the main chain, one first synthesizes a derivatized heterodiamondoid molecule, that is to say, a heterodiamondoid having at least one functional group substituting one of the original hydrogens. As discussed in that application, there are two major reaction sequences that may be used to derivatize heterodiamondoids: nucleophilic (SNI- type) and electrophilic (SE2-type) substitution reactions. SNI -type reactions involve the generation of heterodiamondoid carbocations, which subsequently react with various nucleophiles. Since tertiary (bridgehead) carbons of heterodiamondoids are considerably more reactive than secondary carbons under SNI reaction conditions, substitution at a tertiary carbon is favored. SE -type reactions involve an electrophilic substitution of a C-H bond via a five-coordinate carbocation intermediate. Of the two major reaction pathways that may be used for the functionalization of heterodiamondoids, the SNI -type may be more widely utilized for generating a variety of heterodiamondoid derivatives. Mono and multi-brominated heterodiamondoids are some of the most versatile intermediates for functionalizing heterodiamondoids. These intermediates are used in, for example, the Koch-Haaf, Ritter, and Friedel-Crafts alkylation and arylation reactions. Although direct bromination of heterodiamondoids is favored at bridgehead (tertiary) carbons, brominated derivatives may be substituted at secondary carbons as well. For the latter case, when synthesis is generally desired at secondary carbons, a free radical scheme is often employed. Although the reaction pathways described above may be preferred in some embodiments of the present invention, many other reaction pathways may certainly be used as well to functionalize a heterodiamondoid. These reaction sequences may be used to produce derivatized heterodiamondoids having a variety of functional groups, such that the derivatives may include heterodiamondoids that are halogenated with elements other than bromine (e.g. fluorine), alkylated diamondoids, nitrated diamondoids, hydroxylated diamondoids, carboxylated diamondoids, ethenylated diamondoids, and aminated diamondoids. See Table 2 of the co-pending application "Polymerizable Higher Diamondoid Derivatives" for a listing of exemplary substituents that may be attached to heterodiamondoids. Heterodiamondoids, as well as heterodiamondoid derivatives having substituents capable of entering into polymerizable reactions, may be subjected to suitable reaction conditions such that polymers are produced. The polymers may be homopolymers or heteropolymers, and the polymerizable diamondoid and/or heterodiamondoid derivatives may be co-polymerized with nondiamondoid, diamondoid, and/or heterodiamondoid-containing monomers. Polymerization is typically carried out using one of the following methods: free radical polymerization, cationic, or anionic polymerization, and polycondensation. Procedures for inducing free radical, cationic, anionic polymerizations, and polycondensation reactions are well known in the art. Free radical polymerization may occur spontaneously upon the absorption of an adequate amount of heat, ultraviolet light, or high-energy radiation. Typically, however, this polymerization process is enhanced by small amounts of a free radical initiator, such as peroxides, aza compounds, Lewis acids, and organometallic reagents. Free radical polymerization may use either non-derivatized or derivatized heterodiamondoid monomers. As a result of the polymerization reaction a covalent bond is formed between diamondoid, nondiamondoid, and heterodiamondoid monomers such that the diamondoid or heterodiamondoid becomes part of the main chain of the polymer. In another embodiment, the functional groups comprising substituents on a diamondoid or heterodiamondoid may polymerize such that the diamondoids or heterodiamondids end up being attached to the main chain as side 5/076825 - 25 -
groups. Diamondoids and heterodiamonhdoids having more than one functional group are capable of cross-linking polymeric chains together. For cationic polymerization, a cationic catalyst may be used to promote the reaction. Suitable catalysts are Lewis acid catalysts, such as boron trifluoride and aluminum trichloride. These polymerization reactions are usually conducted in solution at low-temperature. In anionic polymerizations, the derivatized diamondoid or heterodiamdondoid monomers are typically subjected to a strong nucleophilic agent. Such nucleophiles include, but are not limited to, Grignard reagents and other organometallic compounds. Anionic polymerizations are often facilitated by the removal of water and oxygen from the reaction medium. Polycondensation reactions occur when the functional group of one diamondoid or heterodiamondoid couples with the functional group of another; for example, an amine group of one diamondoid or heterodiamondoid reacting with a carboxylic acid group of another, forming an amide linkage. In other words, one diamondoid or heterodiamondoid may condense with another when the functional group of the first is a suitable nucleophile such as an alcohol, amine, or thiol group, and the functional group of the second is a suitable electrophile such as a carboxylic acid or epoxide group. Examples of heterodiamondoid-containing polymers that may be formed via polycondensation reactions include polyesters, polyamides, and poly ethers. In one embodiment of the present invention, a synthesis technique for the polymerization of heterodiamondoids comprises a two-step synthesis. The first step involves an oxidation to form at least one ketone functionality at a secondary carbon (methylene) position of a heterodiamondoid. The heterodiamondoid may be directly oxidized using a reagent such as concentrated sulfuric acid to produce a keto- heterodiamondoid. In other situations, it may be desirable to convert the hydrocarbon to an alcohol, and then to oxidize the alcohol to the desired ketone. Alternatively, the heterodiamondoid may be initially halogenated (for example with N-chlorosuccinimide, NCS), and the resultant halogenated diamondoid reacted with base (for example, KHCO3 or NaHCO3, in the presence of dimethyl sulfoxide). It will be understood by those skilled in the art that it may be necessary to protect the heteroatom in the heterodiamondoid prior to the oxidation step. The second step consists of the coupling two or more keto- heterodiamondoids to produce the desired polymer of heterodiamondoids. It is known in the art to couple diamondoids by a ketone chemistry, and one process has been described as the McMurry coupling process in U.S. Patent Number 4,225,734. Alternatively, coupling may be effected by reacting the keto-heterodiamondoids in the presence of TiCl3, Na, and 1,4-dioxane. Additionally, polymers of diamondoids (adamantanes) have been illustrated in Canadian Patent Number 2100654. One of ordinary skill in the art will understand that because of the large number of oxidation and coupling reaction conditions available, a variety of keto-heterodiamondoids may be prepared with a diversity of configurational, positional, and stereo configurations. In an alternative embodiment, it is desirable to conduct a sequence of oxidation/coupling steps to maximize the yield of a heterodiamondoid polymer. For example, when the desired polymeric heterodiamondoid contains interposing bridgehead carbons, a three step procedure may be useful. This procedure comprises chlorinating an intermediate coupled polymeric heterodiamondoid with a selective reagent such as NCS. This produces a chlorinated derivative with the newly introduced chlorine on a methylene group adjacent to the double bond (or bonds) that were present in the intermediate. The chloro-derivative is convertable to the desired ketone by substitution of the chlorine by a hydroxyl group, and further oxidation by a reagent such as sodium bicarbonate in dimethylsulfoxide (DMSO). Additional oxidation may be carried out to increase ketone yields, the additional treatment comprising further treatment with pyridine chlorochromate (PCC). A schematic illustration of a polymerization reaction between heterodiamondoid monomers is illustrated in FIG. 8 A. A heterodiamondoid 800 is oxidized using sulfuric acid to the keto-heterodiamondoid 801. The particular diamondoid shown at 801 is a tetramantane, however, any of the diamondoids described above are applicable. Again, the symbol "X" represents a heteroatom substitutionally positioned on a lattice site of the diamondoid. The ketone group in this instance is attached to position 802. Two heterodiamondoids 801 may be coupled using a McMurry reagent as shown in step 802. According to embodiments of the present invention, the coupling between two adjacent heterodiamondoids may be made between any two carbons of each respective heterodiamondoid's nuclear structure, and in this exemplary situation the coupling has been made between carbons 803 of diamondoid 806 and carbon 804 of heterodiamondoid 806. It will be apparent to those skilled in the art that this process may be continued; for example, the pair of heterodiamondoids shown generally at 807 may be functionalized with ketone groups on the heterodiamondoids 805 and 806, respectively, to produce the intermediate 808, where two intermediates 808 may couple to form the complex 809. In this maimer, a polymer may be constructed using the individual heterodiamondoids 800 such that n-type material is fabricated. Such a material is expected to be electrically conducting due to the pi-bonding between adjacent heterodiamondoid monomers. In an alternative embodiment, individual heterodiamondoid molecules may be coupled with electrically conductive polymer "linkers" to generate an 77-type heterodiamondoid material. In this context, a linker is defined as a short segment of polymer comprising one to ten monomer segments of a larger polymer. The linkers of the present invention may comprise a conductive polymer such that electrical conductivity is established between adjacent heterodiamondoids in the overall bulk material. Polymers with conjugated pi-electron backbones are capable of displaying these electronic properties. Conductive polymers are known, and the technology of these materials have been described in a chapter titled "Electrically Conductive Polymers" by J.E. Frommer and R.R. Chance in High Performance Polymers and Composites, J.I. Kroschwitx, Ed. (Wiley, New York, 1991), pp. 174 to 219. The conductivity of many of these polmers have been described in this chapter, and compared to metals, semiconductors, and insulators. A typical semiconducting polymer is poly(p-phenylene sulfide), which has a conductivity as high as 103 Siemens/cm2 (these units are identical to Ω^cm"1), and as low as 10"15, which is as insulating as nylon. Polyacetylene is more conducting with an upper conductance of 103 Ω^cm"1, and a lower conductance of about 10"9 Ω^cm"1. According to embodiments of the present invention, heterodiamondoids may be electrically connected to form a bulk n-type material using oligomers of the polymers discussed above. In this instance, an oligomer refers to a polymerization of about 2 to 20 monomers. Thus, an oligomer may be thought of as a short polymer. In this instance, the purpose of the oligomers, and/or linkers, is to electrically connect a number of heterodiamondoids into a three-dimensional structure such that a bulk material having p-type or n-type electrical conductivity may be achieved. Conductive polymers have been discussed in general by J.E. Frommer and R.R. Chance in a chapter titled "Electrically conductive polymers," in High Perfoi'mance Polymers and Composites, J.I. Kroschwitz, ed. (Wiley, New York, 1991), pp. 174-219. To synthesize a conventional conductive polymer, it is important to incorporate moieties having an extended pi-electron conjugation. The monomers that are typically used to synthesize such polymers are either aromatic, or contain multiple carbon-carbon double bonds that are preserved the in the final polymeric backbone. Alternatively, conjugation may be achieved in a subsequent step that transforms the innitial polymer product into a conjugated polymer. For example, the polymerization of acetylene yields a product of conjugated ethylene units, whereas a benzene polymerization produces a chain of covalently linked aromatic units. A catalog of exemplary oligomers (linkers) that may be used to connect heterodiamondoids in an electrically conductive manner are illustrated in FIGS. 9A- N. Typical linkers that have been shown to be electrically conductive are polyacetylene in FIG. 9A, polythiophene in FIG. 9E, and polyparaphenylene vinylene in FIG. 9F. An electrically conductive linker that will be highlighted as an example in the next discussion is polyaniline, the oligomer of which has been depicted in FIG. 9N. A schematic diagram of a heterodiamondoid polymer generated with polyaniline linking groups is depicted in FIG. 10. The polymer of FIG. 10 is only exemplary in that the conductive linker groups between adjacent heterodiamondoids is a polyaniline functionality, but of course the linking group could be any conductive polymer, many of which comprise conductive diene systems. In FIG. 10 a heterodiamondoid 1001 is linked to a heterodiamondoid 1002 via a short segment 5/076825
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of polyaniline oligomer 1003. The same applies for the connection 1004 to the heterodiamondoid 1005 within the same linear chain. The polymer shown generally at 1000 may also contain crosslinks that connect a linear chain 1006 with 1007. This creates a three-dimensional crosslinked polymer with electrical conductivity in a three-dimensional sense. Crosslinked chains 1008 may be used to connect adjacent linear chains 1006 and 1007. A three- dimensional matrix of an electrically conducting diamondoid containing material is thus established. Each heterodiamondoid 1001 and 1002 contains within its structure a heteroatom which is either an electrical donor or electrical accepter. Overall, fabrication of an n-type heterodiamondoid material is achieved. A third method of fabricating 77-type materials is crystallize the heterodiamondoids into a solid, where the individual heterodiamondoids comprising the solid are held together by Nan der Waals forces (also called London or dispersive forces). Molecules that are held together in such a fashion have been discussed by J.S. Moore and S. Lee in "Crafting Molecular Based Solids,"
Chemistry and Industry, July, 1994, pp. 556-559, and are called "molecular solids" in the art. These authors state that in contrast to extended solids or ionic crystals, the prefered arrangement of molecules in a molecular crystal is presumably one that minimizes total free energy, and thus the fabrication of a molecular crystal is controlled by thermodynamic considerations, unlike a synthetic process. An example of a molecular crystal comprising the pentamantane [1(2,3)4] will be discussed next. In an exemplary embodiment, a molecular crystal comprising [1(2,3)4] pentamantane was formed by the chromatographic and crystallographic techniques described above. These aggregations of diamondoids pack to form actual crystals in the sense that a lattice plus a basis may be defined. In this embodiment, the [1(2,3)4] pentamantane is found to pack in an orthorhombic crystal system having the space group Pnma, with unit cell dimensions a = 11.4786, b = 12.6418, and c = 12.5169 angstroms, respectively. To obtain that diffraction data, a pentamantane crystal was tested in a Bruker SMART 1000 diffractometer using radiation of wavelength 0.71073 angstroms, the crystal maintained at a temperature of 90 K. A unit cell of the pentamantane molecular crystal is illustrated in FIG. 11. This diagram illustrates the generalized manner in which diamondoids may pack in order to be useful according to embodiments of the present invention. These molecular crystals display well-defined exterior crystal facets, and are transparent to visible radiation. Referring to FIG. 11, the packing of the [1(2,3)4] pentamantane is illustrated as a stero view of two unit cells 1102 and 1103. Each unit cell of the crystal contains four pentamantane molecules, where the molecules are arranged such that there is one central cavity or pore per unit cell. In some embodiments of the present invention, the cavity 1106 that is created by the packing of the pentamantane unit cells may accommodate small impurities, or may be enlarged to accomodate a transition element metal such as gold. The purpose of including such impurities may be to enhance electrical conductivity. One significant feature of the packing of the [1(2,3)4] pentamantanes illustrated in FIG. 11 is that ap or «-type diamondoid material may be realized with little further processing than isolation using chromatographic techniques. In other words, no functionalization is necessary to polymerize or link up individual diamondoid molecules, and no expensive deposition equipment is needed in this embodiment. Since these crystal are mechanically soft and easily compressible, being held together by Nan der Waals forces, an exterior "mold" may be necessary to support the π-type, electron donating material. The mold may comprise, for example, regions of sp2-hybridized carbon materials. In an alternative embodiment, a heterodiamondoid (or small cluster of several heterodiamonoids) is contemplated to function at a molecular level as quantum devices such in, for example, single electron emitters. Single electron devices are known, and single electron transistors have been discussed in the art. See, for example, U.S. Pat. 6,335, 245, issued to Park et al., and Quantum Semiconductor Devices and Technologies, T.P Pearsall, ed. (Kluwer, Boston, 2000), pp. 8-12. Park discloses that efforts to reduce device size in the semiconductor industry will drive a reduction in the number of electrons present in a channel (e.g., the conducting pathway between the source and drain of a transistor) from about 300 in the year 2010 to no more than 30 in the year 2020. As the number of electrons necessary for operating a device is reduced, statistical variations in electron behavior will become more of a concern. Thus, although single electron transistors have been conceived, there are a number of difficulties to overcome with regard to their implementation, including the ability to fabricate them using present day lithographic techniques. Pearsall reviews several types of single electron transistors, including metal, semiconducting, carbon nanotube, and superconducting single electron transistors. An example of a heterodiamondoid contemplated for use in a single electron emitter is shown in FIG. 12. Referring to FIG. 12, an /z-type heterodiamondoid comprising a tetramantane 1201 with nitrogen heteroatoms is coupled to a similar tetramantane 1202 through a carbon-carbon double bond 1208 as discussed in the polymer section above. The number of heterodiamondoid molecules in this complex may range from about 1 to 10,000. The electron-emitter contemplated by the present embodiments is not restricted to «-type materials. In other words, the emitter (the cathode of the FED) may comprise p- ype materials as well. The/?-type materials act as electron acceptors, and it is desirable to have the number of electron-donating elements greater than the number of electron-accepting elements such that overall, the material is electron-donating. Inclusion of electron-accepting elements in the emitter material is contemplated, in some situations, to give an enhanced control over the number and distribution of the electrons actually emitted. Thus, in FIG. 12, a p-type tetramantane 1203 with boron heteroatoms may be coupled to a similar tetramantane 1204 through a carbon-carbon double bond 1209. Of course, there may be diamondoids present in the cluster as well that do not contain any heteroatoms (not shown in FIG. 12). On a molecular level, the complex of n-type diamondoids 1205 may be coupled to the complex ofp-type diamondoids 1206 to form the complex 1207. Such a molecular complex may function as a single electron emitter. The heterodiamondoids of the present invention offer enhanced reliability, controllability, and reproducibility not available with prior art methods. Properties of n-type diamond To date, the well-known impurity atoms that have been used to dope diamond include boron and nitrogen. Boron is a -type dopant with an activation energy of 0.37 eN. Nitrogen is an 77-type impurity which may be referred to as a deep donor, because it has the energy level 1.7 eN away from the bottom of the conduction band. Because boron and nitrogen are adjacent to carbon in the same row of the periodic table, these atoms have similar sizes, and thus may be readily introduced into the crystal if size considerations only are taken into account. The properties of boron and nitrogen doped diamond, in particular as they relate to ion implantation, have been discussed by R. Kalish and C. Uzan-Saguy in chapter B3.1, titled "Doping of diamond using ion implantation," in Properties, Growth and Applications of Diamond, edited by M. H. Nazare and A. J. Neves (Inspec, London, 2001), pp. 321-330. In the past, greater success has been achieved developing a -type diamond material than an n-type material. Satisfactory doping of diamond with nitrogen has proven to be elusive, although there has been some recent success with hot filament CND methods. Recently it has been demonstrated by CND methods that phosphorus has a donor state in the diamond bandgap, with a reported activation energy ranging from about 0.46 to 0.6 eN. Boron containing diamond exists in nature (it is called type lib natural diamond), and its electrical properties have been studied extensively. These studies show that the activation energy level of the boron accepter is positioned 0.37 eN above the valence band. More recently, boron doped p-type diamonds have been made using both high-pressure high temperature (HPHT) and chemical vapor deposition (CVD) techniques. The best /?-type diamond material made to date has apparently been made by CND epitaxial growth on <100> diamond surfaces. These 9 1" 1 materials have been reported to yield a carrier mobility of 1800 cm N" s" , and a carrier concentration of about 2.3 x 1014 cm"3 at room temperature. It has been postulated that the success of fabricating boron doped j^-type diamond is due to the small size of the boron atom, which enables it to enter the diamond lattice easily. Once inside the lattice it occupies a predominance of substitutional sites (as opposed to interstitial sites), where electrically it acts as an electron accepter. Kalish and Uzan-Saguy summarize the main points about -type diamond by saying that boron is the best studied p-type dopant in diamond. The boron doped materials demonstrate hole mobilities up to 600 cmVN s, and compensation ratios below 5 percent. The optimal annealing scheme was found to be a high temperature anneal at a temperature greater than 1400°C. In contrast to/>-type diamond, 72-type diamond has been more difficult to fabricate. Among the potential substitutional donors for diamond, only nitrogen and phosphorus appear to enter the crystal to contribute to its electrical properties. Both elements may be introduced into diamond during CND growth. Additionally, group I elements occupying interstitial sites, such as sodium and lithium, have been predicted to act as donors with activation energies of 0.1 and 0.3 eN, respectively. The energy of formation for the bonding of nitrogen within the carbon lattice is predicted to be negative, -3.4 eN, in contrast to the high positive energies of formation predicted for phosphorus (10.4 eN), lithium (5.5 eN), and sodium (15.3 eN). This suggests that the solubilities of these elements in diamond is low, with the exception of nitrogen. As with boron, nitrogen also exists substitutionally in natural diamond (type lb diamond), where the impurity has an activation energy of 1.7 eN. Since this is a very high ionization energy, diamond containing nitrogen impurities are electrically insulating at room temperature, and thus these materials cannot be studied by conventional electrical measurement techniques. Using implantation techniques similar to those used for boron, it was found that after annealing about 50 percent of the implanted nitrogen was located in substitutional sites, but that the nature of the depth of the energy level rendered this type of material unsuitable for use at room temperature. Phosphorus has been predicted to act as a shallow donor in diamond, phosphorus having an activation energy of 0.1 eN. Recently, however, phophorus doped diamond has been grown by CND techniques, and Hall effect measurements showed that phosphorus produced a donor level with an ionization energy about 0.5 eN below the bottom of the conduction band. The mobility of carriers in this material was found to be between about 30 and 180 cm2 N"1 s"1, and typical room temperature carrier concentrations were found to be on the order of 1013 to 1014 cm"3. In other studies, it was found that phosphorus occupied substitutional sites about 70 percent of the time following an anneal at 1200°C. Although this appears to be an attractive method of producing n-type diamond, the authors stated that 7t-type electrical activity of ion implanted phosphorus in diamond has not been found. The cause was speculated to be the large size of the phosphorus atom relative to the dimensions of the diamond crystal lattice. The misfit induces a strain in the diamond lattice which appears to attract and create defects with no electrical activity. Attempts have also been made to produce π-type diamond by lithium implantation. In one study, 7z-type conductivity was verified by hot probe measurements, with an activation energy of 0.23 eN. Another study found an activation energy of 0.22 eN. In another study, about 40 percent of the implanted lithium was found to occupy interstitial lattice sites, with 17 percent in substitutional sites, but no clear n-type electrical signal could be found in this case. It was postulated that substitutional lithium acts as accepter, and interstitial lithium behaves as a donor, with possible compensation between the two effects resulting in no electrical activity. A further discussion of boron doped diamond has been given by C. Johnston et al. in chapter B3.3, titled "Boron doping and characterization of diamond," in Properties, Growth and Applications of Diamond, edited by M. H. Νazare and A. J. Νeves (Inspec, London, 2001), pp. 337-344. These authors state that it is known from studies on natural diamond that boron acts as an acceptor with an energy level 0.368 eN above the edge of the valence band. There are essentially three ways to achieve the doping of diamond with boron, and these methods include 1) incorporation of boron in diamond in situ during growth, 2) ex situ by ion implantation, and 3) by high temperature diffusion. One disadvantage with the above mentioned methods is that boron incorporation may be dependent upon the texture of the diamond film or the orientation of the substrate upon which the diamond is being deposited. In one study, the probability of boron incorporation into a growing diamond film having a having <111> orientation was up to one order of magnitude greater than in films having a <100> orientation. The incorporation of dopants into a growing diamond film is also dependent upon the morphology of the deposited material. For example, the average crystallite size was reduced by an order of magnitude when the boron concentration was increased from about 1016 to 1021 cm"3. As discussed above, it is more difficult to prepare 72-type diamond H anp- type diamond by ion implantation, but recently the incorporation of nitrogen and phosphorus into diamond using CND methods have proven to be more successful. Such a technique has been discussed by G.Z. Cao in chapter B3.4, titled "Nitrogen and phosphorus doping in CND diamond," in Properties, Growth and Applications of Diamond, edited by M. H. Νazare and A. J. Νeves (Inspec, London, 2001), pp. 345-347. This author states that diamond promises high power, high frequency, and high temperature electronic applications due to its unique physical properties. These properties include a high carrier mobility of 0.16 m2/N s, a high thermal conductivity of up to about 1.5 x 104 W/m K, and a wide bandgap energy of 5.5 eN. E-type conduction has been demonstrated in both the naturally occurring type lib diamond, as well as synthetic ?-type diamond created by either high pressure, high temperature (HPHT) techniques or by chemical vapor deposition CND techniques. To create 77-type diamond, nitrogen and phosphorus were considered to be possible donor elements. Nitrogen is the most prevalent impurity in naturally occurring diamond, and can be readily incorporated into CND diamond using either Ν2 or NH3 as a precursor. Hot filament CND was the preferred method. Typical concentrations were 6 x 1019 atoms/cm3. However, the rate of incorporation of nitrogen into the growing diamond film was dependent on the orientation of the growing film, and the growth rate of the film was dependent on the amount of nitrogen in the feed gas. For example, (100) facets incorporated the highest concentration of nitrogen into the diamond, followed by (111) facets, with (100) facets incorporating the least amount of nitrogen. However, the addition of nitrogen to the feed gas resulted in the greatest enhancement of growth for (100) facets, followed by (111) facets, with the least enhancement in (110) facets. Cao reiterates that phosphorus is a promising donor candidate for n-type semiconducting diamond films. Modelling has shown that phosphorus may behave as a shallow donor in diamond, having an energy level 0.2 eN from the bottom of the conduction band. However, phosphorus has a large positive energy of formation (10.4 eN), and thus a low equilibrium solubility in diamond. This is in part due to the large size of phosphorus relative to carbon; for example, phosphorus has a radius of 1.10 angstroms compared to the 0.77 angstrom radius of carbon. In early studies of phosphorus doping, only low concentrations of phosphorus doping could be achieved, but it was found that the concentrations of phosphorus could be enhanced in the presence of other impurities, such as boron. Unfortunately, due to the donor-acceptor compensation effect discussed above, no n- type conduction could be achieved. To review: the properties of of the doped diamond depend on the nature of the dopant. Boron doped diamond has an acceptor level of 0.368 eN above the valence band, which may be viewed as a shallow level, and therefore holes may be excited from states within the bandgap to the top of the valence band with relatively low energies. However, nitrogen is a deep donor with an energy level 1.7 eN away from the bottom of the conduction band, and therefore relatively large amounts of energy are required to elevate an electron from a donor state within the conduction band to the bottom of the conduction band. Thus, when 7j-type diamond is doped with diamond, it is not electrically conducting at room temperature because these temperature do not provide enough energy to excite the electron from its energy state state within the bandgap to the conduction band. Phosphorus has been modelled to be a shallow donor with an energy state at 0.2 eN away from the conduction band edge, making phosphorus a potential candidate for an n-type dopant, and lithium is another possiblity. It should be noted that, under some circumstances, the hydrogenated surface of diamond may impart to the crystal a/7-type conductivity. This has been discussed by K. Bobrov et al. in "Atomic-scale imaging of insulating diamond through resonant electron injection," Nature, Nol. 413, pp. 616-619 (2001). This study demonstrated that a scanning tunnelling microscopic technique could be used to image an "insulating" diamond surface to investigate electronics properties at the atomic scale. The hydrogenated surface of a single crystal of (100) diamond could be imaged with STM at a negative sample bias. The hydrogen-free diamond surface was insulating. Embodiments of the present invention circumvent the difficulties of the prior art techniques by synthesizing heterodiamondoids such that the impurity electron donor atom is included in the diamond crystal lattice structure prior to the fabrication of the n-type semiconducting material. Such n-type heterodiamondoid materials may be used in devices, for example, field emission devices.
Field emission devices According to embodiments of the present invention, a heterodiamondoid or heterodiamondoid-containing material is utilized as a cold cathode filament in a field emission device suitable for use, among other places, in flat panel displays. The unique properties of a heteroatom-containing diamondoid make this possible. These properties include the negative electron affinity of a hydrogenated diamond surface, in conjunction with the small size of a typical higher diamondoid molecule. The latter presents striking electronic features in the sense that the diamond material in the center of the diamondoid comprises high purity diamond single crystal, with the existence of significantly different electronic states at the surface of the diamondoid. These surface states may make possible very long diffusion lengths for conduction band electrons. An electron-donating heteroatom, such as nitrogen for example, contributes electrons to the conduction band of the material to facilitate electron emission from the cathode. In a chapter entitled "Novel Cold Cathode Materials," in Vacuum Microelectronics (Wiley, New York, 2001), pp. 247-287, written by W. Zhu et al, the current requirements for a microtip field emitter array are given, as well as the properties an improved field emission cathode are expected to deliver. Perhaps the most difficult problem presented by a conventional field emission cathode is the high voltage that must be applied to the device in order to extract electrons from the filament. Zhu et al. report a typical control voltage for microtip field emitter array of about 50-100 volts because of the high work function of the material typically comprising a field emission cathode. Diamonds in general, and in particular a hydrogenated diamond surface, offer a unique solution to this problem because of the fact that a diamond surface displays an electron affinity that is negative. The electron affinity of the material is a function of electronic states at the surface of the material. When a diamond surface is passivated with hydrogen, that is to say, each of the carbon atoms on the surface are sp3 -hybridized, i.e., bonded to hydrogen atoms, the electron affinity of that hydrogenated diamond surface surface can become negative. The remarkable consequence of a surface having a negative electron affinity is that the energy barrier to an electron attempting to escape the material is energetically favorable and in a "downhill" direction. Diamond is the only known material to have a negative electron affinity in air. In more specific terms, the electron affinity χ of a material is negative, where χ is defined to be the energy required to excite an electron from an electronic state at the minimum of the conduction band to the energy level of a vacuum. For most semiconductors, the minimum of the conduction band is below that of the vacuum level, so that the electron affinity of that material is positive. Electrons in the conduction band of such a material are bound to the semiconductor by an energy that is equal to the the electron affinity, and this energy must be supplied to the semiconductor to excite and electron from the surface of that material. It should be noted that a field emission cathode comprising a diamond filament may suffer from an inherent property: while electrons in the conduction band are easily ejected into the vacuum level, exciting electrons from the valence band into the conduction band to make them available for field emission may be problematic. This is because of the wide bandgap of diamond. In a normal situation, few electrons are able to traverse the bandgap, in other words, move from electronic states in the valence band to electronic states in the conduction band. Thus, diamond is generally thought to be unable to sustain electron emission because of its insulating nature. To reiterate, although electrons may easily escape into the vacuum from the surface of a hydrogenated diamond film, due to the negative electron affinity of that surface, the problem is that there are no readily available mechanisms by which electrons may be excited from the bulk into electronic surface states. There may be several ways to circumvent this problem. Observations of electron emission from diamond surfaces have either: 1) a high defect density, such as a relatively large inclusion of elemental nitrogen, or 2) an unusual microstructure including vapor-deposited islands or a film having a nanocrystalline morphology. They can also demonstrate quantum mechanically tunneling. It is known in the art that diamond materials with small grain sizes and high defect densities generally emit electrons more easily than diamond materials with large crystalline sizes and low defect defect concentrations. It has been reported (see the Zhu reference above) that outstanding emission properties are seen in ultrafϊne diamond powders containing crystallites having sizes in the range of 1 to 20 nm. Emission of electrons has been found to originate from sites that are associated with defect structures in diamond, rather than sharp features associated with the surface, and that compared with conventional silicon or metal microtip emitters, diamond emitters show lower threshold fields, improved emission stability, and robustness and vacuum environments. According to embodiments of the present invention, a field emission cathode comprises a heterodiamondoid, a derivatized heterodiamondoid, a polymerized heterodiamondoid, and all or any of the other diamondoid containing materials discussed in previous sections of this description. According to further embodiments of the present invention, the heteroatom of the heterodiamondoid is an electron-donating species such as nitrogen. An exemplary field emission cathode comprising a heterodiamondoid is shown in FIG. 13. Referring to FIG. 13, a field emission device shown generally at 1300 comprises a heterodiamondoid-containing filament 1301, which acts as a cathode for the device 1300, and a faceplate 1302 on which a phosphorescent coating 1303 has been deposited. The anode for the device may be either a conductive layer 1304 positioned behind the phosphorescent coating 1303, or an electrode 1305 positioned adjacent to the filament 1301. During operation, a voltage from a power supply 1306 is applied between the filament electrode 1307, and the anode of the device, either electrode 1304 or 1305. A typical operating voltage (that is, the potential difference between the cathode and the anode) is less than about 10 volts. This is what allows the cathode to be operated in a so-called "cold" configuration. A typical electronic affinity for a diamondoid surface is contemplated to be less than about 3 eN, and in other embodiments it may be negative. An electron affinity that is less than about 3 eN is considered to be a "low positive value." Although a diamond material is generally thought to be electrically insulating, the heterodiamondoid filament (or cathode) 1301 contains an electron- donating heteroatom 1310, which may be any column N (TUPAC notation) or column NI element such as Ν, P, As, or O, S, Se, respectively. These electron- donating elements contribute one electron (for the column N case) or two electrons (for the column NI case) to the conduction band of the material comprising the heterodiamondoid-containing cathode. Additionally, the cathode may be dimensionally small enough to allow electrons to tunnel (in a quantum mechanical sense) from the filament electrode 1307 to an opposite surface of the heterodiamondoid, which may be the surface 1308 or the tip 1309. It will be appreciated by the skilled in the art that it is not essential for the heterodiamondoid filament 1301 to have an apex or tip 1309, since the surface of the diamondoid is hydrogenated and sp3-hybridized. In an alternative embodiment, the surface of the cathode 1301 may comprise a heterodiamondoid-containing material that is at least partially derivatized such that the surface comprises both sp2 and sp3 -hybridization. In the present embodiments, the electron affinity of the cathode is less than about 3 eN, and may be negative. Tthe heterodiamondoid content of the cathode 1301 may range from about 1 to 100 percent by weight for the heterodiamondoid-containing component, whether the heterodiamondoid-containing component is a product of a CND reaction, a polymer, a molecular crystal, or a cluster of individual heterodiamondoids. Furthermore, the form of the heterodiamondoid-containing material may include fiber or film shapes. The surface of the heterodiamondoid-containing material may comprise carbon atoms that are substantially sp3 -hybridized, but the surface may also be derivatized or co-crystallized such that the surface comprises both sp2 and sp3-hybridized carbon. An advantage contemplated by this embodiment of the present invention is that a greater resolution of the device may be realized relative to a conventional field emission device because of the greater number of electrons that may be emitted, the small size of a typical heterodiamondoid, and the more repeatable and uniform structure available with the use of heterodiamondoids.
EXAMPLES The following examples show methods of synthesizing nitrogen and boron containing heterodiamondoids, and polymerized heterodiamondoids, in accordance with embodiments of the present invention. They are intended to be examples and are not to be viewed as limiting the invention as claimed below. Examples 1-3 describe methods that could be used to prepare nitrogen containing heterodiamondoids; e.g. azadiamondoids. Example 4 discloses exemplary methods of preparing polymers from heterodiamondoids, including polymers comprising heterodiamondoids coupled through double bonds between diamondoid lattice site carbons. Example 1 demonstrate the preparation of aza tetramantanes from a feedstock which contains a mixture of tetramantanes including some alkyltetramantanes and other impurities. Other feedstocks containing different diamondoids (such as triamantane, or tetramantane and higher diamondoids) may also be applicable and produce similar heterodiamondoid mixtures.
Example 1 Aza tetramantanes from a feedstock containing a mixture of tetramantane isomers In the following example, a mixture of aza tetramantanes was prepared from a feedstock containing a mixture of the three tetramantane isomers wo-tetramantane, αntz-tetramantane, and s/ ew-tetramantane. A first step in this exemplary synthesis involved the photo-hydroxylation of a feedstock containing tetramantanes. The feedstock may be obtained by methods described in U.S. Patent Application 10/052,636, filed January 17, 2002, and incorporated herein by reference in its entirety. A fraction containing at least one of the tetramantane isomers was obtained, and the fraction may have included substituted tetramantanes (such as an alkyltetramantane) and hydrocarbon impurities as well. The gas chromatagraphy/mass spetrometry (GC/MS) of the composition of this fraction showed a mixture of tetramantanes. A solution of 200 mg of the above feedstock containing tetramantanes in 6.1 g of methylene chloride was mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate. While being stirred vigorously, the solution was irradiated with a 100-watt UN light. Gas evolution was evident from the start. The temperature was maintained at 40-45°C for an irratiation period of about 21 hours. Then the solution was concentrated to near dryness, treated twice in succession with 10-mL portions of toluene, and reevaporated to dryness. The product was then subjected to GC/MS characterization to show the presence of hydroxylated tetramantane isomers. In an alternative embodiment, the tetramantane feedstock may be oxidized directly according to the procedures of McKervey et al. (see J. Chem. Soc, Perkin Trans. 1, 1972, 2691). The crude product mixture is then subjected to GC/MS characterization to show the presence of iso-tetramantones. The oxidized feedstock as prepared by direct oxidation, wherein the product contains tetramantones, is then reduced with lithium aluminum hydride in ethyl ether at a low temperature. After completion of the reaction, the reaction mixture is worked up by adding saturated Νa2SO4 aqueous solution to decompose excess lithium aluminum hydride at a low temperature. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude product. The crude product may be characterized by GC/MS to show the presence of hydroxylated tetramantane isomers. In the next step, an azahomo tetramantane-ene may be produced from the above hydroxylated tetramantanes, or from photooxidized tetramantanes. To a stirred and ice cooled mixture of 98% methanesulfonic acid (1.5 ml) and dichloromethane (3.5 ml) was added solid sodium azide (1.52 g, 8.0 mmol). To that mixture was added the hydroxylated tetramantanes as prepared above. To this resulting mixture was added in small increments sodium azide (1.04 g, 16 mmol) over a period of about 0.5 h. Stirring was continued for about 8 h at 20-25 °C, and then the mixture was poured into ice water (ca. 10 ml). The aqueous layer was separated, washed with CH2C12 (3 ml), basified with 50% aqueous KOH-ice, and extracted with CH C12 (10 mlx4). The combined extracts were dried with Na2SO4, and the solvent was removed to afford a brownish oil product. The product was characterized by GC/MS to show the presence of azahomo tetramantane-ene isomers. In the next step, an epoxy azahomo tetramantane was made from the azahomo tetramantane-enes via the following procedure. The above mixture was treated with -CPBA (1.1 equ.) in CH2Cl2-NaHCO3 at a temperature of about 20°C for about 12 h, and the reaction mixture was then worked up with a CH2C12 extraction to afford a crude product that was characterized by GC/MS to show the presence of epoxy azahomo tetramantanes. In the next step, a mixture of N-formyl aza tetramantanes was prepared from the epoxy azahomo tetramantane mixture by irradiating the epoxy aza tetramantane mixture in cyclohexane using a high intensity Hg lamp for about 0.5 hours. The reaction was carried out in an argon atmosphere. Generally speaking, a simpler reaction product was obtained if the reaction was allowed to proceed for only a short time; longer periods gave a complex mixture. The initial product was characterized by GC/MS as a mixture of N-formyl aza tetramantanes. In a final step, aza tetramantanes was prepared from the above described N- formyl aza tetramantanes by mixing the N-formyl aza tetramantanes with 10 mL of 15% hydrochloric acid. The resultant mixture was heated to a boil for about 24 hours. After cooling, the mixture was subjected to a typical workup to afford a product which was characterized by GC/MS showing the presence of aza tetramantanes.
Example 2 Preparation of aza iso-tetramantane from iso-tetramantane In this example, an aza wo-tetramantane is prepared from a single tetramantane isomer, wo-tetramantane, as shown in FIGS. 5A-B. As with the mixture of tetramantanes, this synthetic pathway also begins with the photo- hydroxylation of zso-tetramantane or chemical oxidation/reduction to the hydroxylated compound 2a shown in FIG. 5 A. A solution of 3.7 mmol wo-tetramantane in 6.1 g of methylene chloride is mixed with 4.22 g of a solution of 1.03 g (13.5 mmol) of peracetic acid in ethyl acetate. While stirring vigorously, the solution is irradiated by a 100-watt UN light, and gas evolution is evident as soon as the irridation process is started. The temperature is maintained at 40-45 °C for an irradiation period of about 21 -hours. The solution is then concentrated to near dryness, treated twice in succession with 10-mL portions of toluene, and reevaporated to dryness. The crude product containing a mixture of iso-tetramantanes hydroxylated at the C-2 and C-3 positions is not purified; instead, the mixture is used directly in a reaction comprising the oxidation of the hydroxylated compound 2 a to a keto compound 1. The photo-hydroxylated tsO-tetramantane containing a mixture of C-2 and C- 3 hydroxylated i-o-tetramantanes is partially dissolved in acetone. The oxygenated components go into solution, but not all of the unreacted t,sO-tetram.antane is capable of being dissolved. A solution of chromic acid and sulfuric acid is then added dropwise until an excess of the acid is present, and the reaction mixture is stirred overnight. The acetone solution is decanted from the precipitated chromic sulfate and unreacted iso-tetramantane, and dried with sodium sulfate. The unreacted iso- tetramantane is recovered by dissolving the chromium salts in water with subsequent filtering. Evaporation of the acetone solution affords a white solid. The crude solid is chromatographed on alumina using conventional procedures, where it may be eluted initially with 1 : 1 (v/v) benzene/light petroleum ether followed by either ethyl ether or by a mixture of ethyl ether and methanol (95:5 v/v), in order to collect first the unreacted wo-tetramantane and then the keto compound 1. Further purification by recrystallization from cyclohexane may afford a substantially pure product 1. Alternatively, wσ-tetramantane may be directly oxidized to the keto compound 1 according to the procedures of McKervey et al. (J. Chem. Soc, Perkin Trans. 1, 1972, 2691). Following the oxidation step, the ketone compound 1 may be reduced to a C-2 hydroxylated wo-tetramantane 2a by treating the ketone compound 1 with excess lithium aluminum hydride in ethyl ether at low temperatures. After completion of the reaction, the reaction mixture is worked up by adding at a low temperature a saturated Νa2SO4 aqueous solution to decompose the excess hydride. Decantation from the precipitated salts gives a dry ether solution, which, when evaporated, affords a crude monohydroxylated iso-tetramantane substituted at the secondary carbon. This compound may be described as a C-2 tetramantan-ol. Further recrystallization from cyclohexane gives a substantially pure product. Alternatively, a C-2 methyl hydroxyl iso-tetramantane 2b may be prepared from the keto compound 1 by adding dropwise to a stirred solution of keto compound 1 (2 mmol) in dry THF (20 mL) at -78 °C (dry ice/methanol) a 0.8 molar solution (2.8 mL, 2.24 mmol) of methyllithium in ether. The stirring is continued for about 2 hours at -78°C, and for another 1 hour at room temperature. Then, saturated ammonium chloride solution (1 mL) is added, and the mixture extracted with ether (2x30 mL). The organic layer is dried with sodium sulfate and concentrated to give the product 2b, which is subsequently purified by either chromatography or recrystallization. In the next step, the azahomo wo-tetramantane-ene 3 is prepared from the hydroxylated compound 2. To a stirred and ice-cooled mixture of 98% methanesulfonic acid (15 mL) and dichloromethane (10 mL) is added solid sodium azide (1.52 g, 8.0 mmol), and then either the above C-2 hydroxylated compound 2a or 2b (6 mmol). To the resulting mixture is added in small increments sodium azide (1.04 g, 16 mmol) during a 0.5 hour period. After addition of the sodium azide the stirring is continued for about 8 hours at about 20 to 25°C. The mixture is is then poured onto ice water (ca. 10 mL). The aqueous layer is separated, washed with
CH2C12 (3 mL), basified with 50% aqueous KOH-ice, and extracted with CH2C12 (10 mLx4). The combined extracts are dried (Na2SO4), and the solvent is removed to afford a brownish oil, which is subjected to chromatography purification to afford a substantially pure sample 3 (3a or 3b). In the next step, an epoxy azahomo wo-tetramantane 4 is prepared from azahomo wo-tetramantane-ene 3. A mixture of the azahomo zsO-tetramantane-ene 3 (3a or 3b) with 7W-CPBA (1.1 equ.) in CH2Cl2-NaHCO3 is stored at 5-20°C, followed by the usual workup and short column chromatography gives the epoxy azahomo wo-tetramantane 4 (4a or 4b). In the next step, N-acyl aza wo-tetramantane 5b is prepared from the epoxy azahomo wo-tetramantane 4b by irradiating the epoxy azahomo zsø-tetramantane 4b in cyclohexane for about 0.5 hours with a UN lamp. The radiation passes tlirough a quartz filter and the reaction is carried out under an argon atmosphere. Generally speaking, a single product is formed when the reaction is allowed to proceed for only a short time: longer periods gives a complex mixture of products. Products may be isolated by chromatographic techniques. Ν-formyl aza 5a can be similarly prepared from the epoxy azahomo tsø-tetramantane 4a. In the next step, the aza tsø-tetramantane 6 is prepared from Ν-acyl aza- isotetramantane 5b by heating the Ν-acyl aza zso-tetramantane 5b (5 mmol) to reflux for about 5 hours with a solution of 2 g powdered sodium hydroxide in 20 mL diethylene glycol. After cooling, the mixture is poured into 50 mL water and extracted with ethyl ether. The ether extract is dried with potassium hydroxide. The ether is distilled off to afford the product aza tsø-tetramantane 6. The hydrochloride salt is generally prepared for analysis. Thus, dry hydrogen chloride is passed into the ether solution of the amine, whereby the salt separates out as a crystalline compound. The salt may be purified by dissolving it in ethanol, and precipitating with absolute ether. Typically, the solution is left undisturbed for several days to obtain complete crystallization. Alternatively, the aza tsO-tetramantane 6 may be prepared from the Ν-formyl aza tsø-tetramantane 5a by mixing the Ν-formyl aza zsø-tetramantane 5a (2.3 mmol) with 10 mL of 15% hydrochloric acid. The resultant mixture is heated to a boil for about 24 hours. After mixture is then cooled, and the precipitate filtered and recrystallized from isopropanol to afford the product aza tSO-tetramantane 6. Example 3 Preparation of the aza iso-tetramantane 6 product by fragmentation of a keto compound 1 to an unsaturated carboxylic acid 7 An alternative synthetic pathway for the preparation of the product aza iso- tetramantane 6 is shown in FIG. 5B. Referring to FIG. 5B, the wø-tetramantone 1 as prepared above may be fragmented to the unsaturated carboxylic acid 7 by an abnormal Schmidt reaction per McKervey et al. (Synth. Comrnun., 1973, 3, 435). It is contemplated that this synthesis is analagous to that reported in the literature for adamantane and diamantane (see, for example, Sasaki et al., J. Org. Chem., 1970, 35, 4109; and Fort, Jr. et al, J. Org. Chem., 1981, 46(7), 1388). In the next step, the compound 8 may be prepared from the carboxylic acid 7. To 4.6 mmol of the carboxylic acid 7 is added 12 mL of glacial acetic acid and 3.67 g (4.48 mmol) of anhydrous sodium acetate. The mixture is stirred and heated to about 70°C. Lead(IN) acetate (3.0 g, 6.0 mmol, 90% pure, 4% acetic acid) is added in three portions over 30 min. Stirring is continued for 45 min at 70°C. The mixture is then cooled to room temperature and diluted with 20 mL of water. The resulting suspension is stirred with 20 mL of ether, and a few drops of hydrazine hydrate are added to the dissolve the precipitated lead dioxide. The ether layer is then separated, washed several times with water, washed once with saturated sodium bicarbonate, and dried over anhydrous sodium sulfate. Removal of the ether gives an oily material from which a mixture of the two isomers (exo- and endo-) of compound 8 is obtained. Further purification and separation of the stereochemical isomers (exo- and endo-) can be achieved by distillation under vacuum. Compound 9 (exo- or endo-) may then be prepared from compound 8 (exo- or endo-) by adding to a solution of compound 8 (0.862 mmol) in 5 mL of anhydrous ether 0.13 g (3.4 mmol) of lithium aluminum hydride. The mixture is refluxed with stirring for about 24 hours. Excess lithium aluminum hydride is destroyed by the dropwise addition of water, and the precipitated lithium and aluminum hydroxides are dissolved in excess 10% hydrochloric acid. The ether layer is separated, washed with water, dried over anhydrous sodium sulfate, and evaporated to give compound 9 (which will be a mixture of exo-9 and endo-9 isomers if the starting material was a mixture of exo-8 and endo-8). Further purification may be achieved by recrystallization of the product from methanol- water. Compound 10 is then prepared from an exo- and endo- mixture of compound 9. A solution of a mixture of the alcohols 9 (1.05 mmol) in 5 mL of acetone is stirred in an Erlenmeyer flask at 25°C. To this solution is added dropwise 8 Ν chromic acid until the orange color persists; the temperature is maintained at 25°C. The orange solution is then stirred at 25°C for an addition period of about 3 hours. Most of the acetone is removed, and 5 mL of water is added to the residue. The aqueous mixture is extracted twice with ether, and the combined extracts are washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, and evaporated to give crude compound 10. Sublimation on a steam bath gives substantially pure 10. In an alternative embodiment, the compound 10 may be prepared from an individual isomer of the compound 9, as opposed to the mixture of exo- and endo-9 isomers. For example, compound 10 may be prepared from exo-9 by stirring a solution of exo-9 (1.05 mmol) in 5 mL of acetone in an Erlenmeyer flask at 25°C. To this solution is added dropwise 8 N chromic acid until the orange color persists, the temperature being maintained at about 25°C. The orange solution is then stirred at 25°C for about 3 hours. Most of the acetone is removed, and 5 mL of water is added to the residue. The aqueous mixture is extracted twice with ether, and the combined extracts are washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, and evaporated to give crude 10. Sublimation on a steam bath gives substantially pure 10. In another alternative embodiment, compound 10 may be prepared directly from the carboxylic acid 7, rather than through intermediate compounds 8 and 9. To this end, a solution of the carboxylic acid 7 (4.59 mmol) in 15 mL of dry THF is stirred under dry argon and cooled to 0°C. A solution of 1.5 g (13.76 mmol) of lithium diisopropylamide in 25 mL of dry THF under argon is added through a syringe to the solution of 7 at such a rate that the temperature does not rise above about 10°C. The resulting solution of the dianion of 7 is stirred at 0 °C for about 3 hours. It is then cooled to about -78°C with a dry ice-acetone bath, and dry oxygen is bubbled slowly through the solution for about 3 hours or more. A mixture of about 10 mL of THF and 1 mL water is added to the reaction mixture, which is then allowed to warm to room temperature and is stirred overnight. The solution is concentrated to about 10 mL under vacuum, poured into excess 10% HC1, and extracted with ether. The ether layer is washed with 5% NaOH to remove unreacted 7, which may be recovered by acidification of the basic wash. The ether layer is dried over anhydrous sulfate and stripped to yield crude 10. Sublimation on a steam bath at 3-5 torr gives substantially pure product. Referring again to FIG. 5B, compound 11 may be prepared from compound 10 in the following manner. To a solution of compound 10 (1.6 mmol) in a mixture of pyridine and 95% ethanol (1:1) is added 250 mg (3.6 mmol) of hydroxylamine hydrochloride, and the mixture is stirred at reflux for about 3 days. Most of the solvent is evaporated in a stream of air, and the residue is taken up in 25 mL of water. An ether extract of the aqueous solution is washed with 10% HC1 to extract the oxime 11. Neutralization of the acid wash with 10% sodium hydroxide precipitate the oxime 11, which is filtered off and recrystallized from ethanol- water. In a final step, the aza wø-tetramantane 6 is prepared from compound 11 by the dropwise addition of a solution of compound 11 (0.98 mmol) in 25 mL of anhydrous ether to a stirred suspension of 250 mg (6.58 mmol) of lithium aluminum hydride in 25 mL of anhydrous ether. The mixture is stirred at reflux for about 2 days. Excess lithium aluminum hydride is destroyed with water, and the precipitated lithium and aluminum hydroxides are dissolved in excess 25% sodium hydroxide. The resulting basic solution is extracted twice with ether, and the combined extracts are then washed with 10% HC1. Neutralization of the acidic wash with 10% sodium hydroxide precipitates product 6, which is extracted back into fresh ether. The ether solution is dried over anhydrous sodium sulfate and stripped. The crude product is purified by repeated sublimation on a steam bath under vacuum.
Example 4 Preparation of polymeric heterodimondoids coupled by double bonds between carbons on diamond lattice positions This example describes an exemplary method that may be used to prepare polymeric heterodimondoids coupled by double bonds between carbon atoms positioned on diamond lattice positions of adjacent heterodiamondoids. In this example, many different configuration of polymeric heterodiamondoids may be prepared, including cyclic, linear, and zig-zag polmers, depending on the positions of the carbon atoms within the diamondoid itself. It will be understood by those skilled in the art that there may be a substantially unlimited number of configurations that may be prepared using the methodology of the present embodiments, but a specific oxidation reaction will be described next, and the coupling reaction is described in Example 9. Hetero-diamondoidone (keto-heterodiamondoid) is prepared by adding 10 mmoles of hetero-diamondoid to 100 mL of 96% sulfuric acid. The reaction mixture is then heated for about five hours at about 75 °C with vigorous stirring. Stirring is continued at room temperature for about one additional hour. The black reaction mixture is poured over ice and steam distilled. The steam distillate is extracted with ether, and the combined ether extracts are washed with water and dried over MgSO4. Ether is evaporated to yield a crude product mixture. Chromatography on alumina separates the unreacted hetero diamondoid to yield the ketone fraction (eluting with petroleum or other suitable solvent) and by-product alcohol fraction (eluting with ether or other suitable solvent). The yield of the ketone (mixture of different positional and stereo isomers) is generally about 20%. It will be understood by those skilled in the art that some heteroatoms in the heterodiamondoids may need to be protected before being subjected to the oxidation/coupling reactions described herein. The by-product alcohols from oxidations with strong oxidizing agents such as H2SO4 or from direct oxidation products of milder oxidations such as with t- butylhydroperoxide can be converted to ketones by treating with H2SO4 as follows. The alcohol dissolved in 96% H2SO4 is stirred vigorously at 75°C for about 4.5 hours in a loosely stoppered flask with occasional shaking. After about 5 hours the reaction is quenched and worked up as above. The total ketone yields are generally about 30%. Example 5
Preparation of Ketone Compounds with the Ketone Groups Introduced into Double Bond Coupled Hetero Diamondoids with High Selectivity on Methylene Groups Adjacent to the Double Bonds Linking the Diamondoids To a solution of 1 mmol of the double bond coupled heterodiamondoid in 20 mL of CH2C12 is added 1.05 mmol (140 mg) of NCS. The reaction mixture is stirred for about 1 hour at room temperature, diluted with CH2C12, and washed twice with water. The organic layer is dried over MgSO4 and evaporated. The chlorinated products (mixture of different positional or stereo isomers) are produced. The intermediate chlorides are converted to a mixture of the corresponding alcohols and ketones by heating them to around 100 °C in solution of sodium bicarbonate in DMSO for several hours. The product mixture is partitioned between hexane and water and the hexane layer evaporated to yield the product mixture. Conversion of the remaining alcohols to ketones is accomplished by refluxing with a 0.15 mol solution of PCC while stirring for about 2 hours. The ketones are isolated by adding a large excess of diethyl ether to the cooled mixture and washing all solids with additional ether. The ether solution is passed through a short pad of Florisil and the ether evaporated to yield the ketone products with different positional or stereo isomers which may be separated and used for subsequent coupling reactions. High selectivity for ketone introduction adjacent to double bonds can also be accomplished by selective bromination as shown following: to a solution of 3 mmol of the double bond coupled heterodiamondoid in 40 mL of CH C12 is added 6.6 mmol (1.175 g) of N-bromosuccinimide (NBS). The reaction mixture is refluxed and stirred for about 12 hours. The reaction mixture is diluted with CH2C12 and washed twice with water and a saturated Na2S2O3 solution. The organic layer is dried over MgSO4 and evaporated. The yield of the brominated products is about 90%. Conversion of this intermediate to ketone products is accomplished using the same procedure above.
Example 6 Preparation ofDϊketones of Heterodiamondoids Diketones of heterodiamondoids can be produced by more vigorous oxidation than the above examples (Examples 4 and 5) using strong oxidizing agents such as H2SO4 or CrO3/Ac20 but are preferably produced by a sequence of oxidations. First to monoketones or hydroxyketones followed by further oxidation or rearrangement-oxidation, depending on the intermediates involved. The monoketones are generally treated with a solution of CrO3 in acetic anhydride at near room temperature for about 2 days. The reaction is quenched with dilute aqueous caustic (NaOH), and the product isolated by extraction with diethyl ether. The product diketones are then separated and used for coupling reactions.
Example 7 Preparation of Adjacent Ketones on the Same Heterodiamondoid Face A particularly useful oxidation procedure to produce adjacent ketones on the same diamondoid face is to selectively oxidize an intermediate ketone with SeO /H2O2 to a lactone, then rearrange the lactone to an hydroxyketone with strong acid and oxidize that hydroxyketone to the desired diketone. For example, a monoketone heterodiamondoid is treated at elevated temperature with a 1.5 molar excess of SeO2 in 30% H2O2 at around 60 °C for several hours. The mixed lactone products are isolated by dilution of the reaction solution with water, extraction with hexane and removal of the hexane by evaporation. The lactones are hydrolyzed and rearranged by heating with 50% H2SO4. Again the products are isolated as above and further converted to a mixture of positional diketone isomers which are isolated and used for further coupling reactions.
Example 8 Preparation of Mixed Keto-Heterodiamondoids In some embodiments it may be desirable to produce polymeric heterodiamondoids linked with double bonds via coupling reactions of heterodiamondoid ketones from mixtures of heterodiamondoids. Thus a composition containing a mixture of heterodiamondoids (heterotetramantanes, heteropentamantanes, and the like) is oxidized to produce a mixture of ketones by treatment with 96% H2SO4 at about 75 °C for about 10 hours or by treating with CrO /Ac2O at near room temperature for about one day. Isolation of the product ketones is accomplished using the procedures described above and are used to prepare mixed polymeric heterodiamondoids by the coupling reaction as described in the next example. Example 9 Preparation of Polymeric Heterodiamondoids by Coupling Their Keto Derivatives Polymeric heterodiamondoids can be made by coupling their keto derivatives using several procedures. One very useful procedure is the McMurray coupling reaction as described next. Preparation of the reagent (M) (with Mg, K, or Na reducing agent, with Na being the most preferred reducing agent) may be carried out by weighing in a glovebox 20 mmol TiCl3 into a three-necked flask. Then 60 mL of dry solvent (for example, THF) is added. To the stirred slurry the desired amount (generally about 30 to 100 mmol) of Grignard magnesium is added from a Schlenk- tube under argon. The mixture is refluxed for about 3 hours, at which time all the Mg has reacted and the color of the mixture has changed from violet via blue, green, and brown to black. Instead of Mg, an equivalent amount of K, freshly cut and washed with hexane, can be used. The reduction is then complete after a reflux time of about 12 hours. To prepare the reagent (M) with the LiAlH4 reducing reagent, the TiCl3/THF mixture is cooled to about 0°C, and the desired amount (generally 15 to 50 mmol) of LiAlH4 is added in small portions to keep the vigorous reaction (H evolution) under control. After the addition, the reaction mixture is stirred at 0°C for about 0.5 hour. If hydrogenation as a side reaction is to be minimized, the black suspension of (M) is refluxed for an additional hour. The coupling reaction is carried out as follows: the desired amount of ketone (generally 10 to 20 mmol of ketone groups) is added to the cooled, black suspension of (M). A rapid evolution of H2 is observed particularly with LiAlH4 as the reducing agent. After the addition, the mixture is stirred at room temperature for 6 to 20 hours depending on the particular diamondoid being coupled. During the reaction a gentle stream of argon is maintained. Experiments have shown that the above reaction times are sufficient to obtain complete coupling. The reaction is then quenched by adding 40 mL of 2N hydrochloric acid, and the reaction mixture is extracted three times with 10 mL of CHC13. The combined organic layers are dried over MgSO4, and the solvent evaporated to yield the polymeric hetero higher diamondoids with yields of about 80%. Purification of the products can be accomplished by column chromatography over Al2O3 eluting with suitable solvent for example petroleum ether and recrystallization from suitable solvent. Using this procedure, the intermediate ketones can be coupled in high yield to produce dimers. Mixed dimers result if two different keto hetero diamondoids are co-coupled. In addition, higher polymeric products form on coupling of multisubstituted hetero diamondoids such as linear rigid rod polymers are formed which have lower solubility and higher melting points than the corresponding zigzag polymers. Under special conditions such as high dilution coupling (keto diamondoid concentrations <0.01 molar), cyclic polymeric hetero higher diamondoids can be formed from the diketones that allow ring closure. Generally tetramers are preferred in these cyclization but cyclic trimers also form in special cases. It will be understood by those skilled in the art that it is possible to produce polymeric heterodiamondoids from different keto-heterodiamondoids, their different positional isomers and stereo isomers under this coupling conditions. Two dimensional sheet polymers can be formed from heterodiamondoids bearing more than 2 ketone groups. Such precursors can be formed by extended oxidations of the parent hetero diamondoids, or by sequential oxidation/couplings as described in the above examples. Cyclic tetramers are particularly useful as intermediates in the production of two dimensional sheets through additional oxidation/coupling sequences as described in the previous examples. In addition to polymerization using the McMurray coupling reaction other methods of forming double bonds between hetero diamondoids are useful. Another very useful procedure also uses ketones as an intermediate. This method consists of condensing heterodiamondoid (G) ketones with hydrazine to form azines (G=N- N=G), addition of H2S to this azine to form a bisdiamondoid thiadiazolidine, oxidation of this intermediate to a bisdiamondoid thiadiazine and finally elimination of the N and S heteroatoms to produce the desired coupled product (G=G). This procedure is useful as it allows one to systematically produce mixed coupled diamondoid polymers by sequential reaction of one hetero diamondoid then another with hydrazine to form mixed azines. The removal of byproducts from the coupled hetero diamondoids is also easier. The following is an example of the coupling of heterodiamondoids via this route. To form the azine, a solution of hydrazine hydrate (98%, 1.30 g, 26 mmol) in 15 mL of tert-butyl alcohol is added dropwise under nitrogen over a period of about 45 minutes to a stirred refluxing solution of a heterodiamondoidone (35 mmol) in 60 mL of tert-butyl alcohol. After the addition is complete, the solution is refluxed for about an additional 12 hours and subsequently allowed to stand at ambient temperature for about 24 hours. The solvent is removed to give an crystalline mass ti which is added 200 mL of water. The aqueous mixture is extracted with ether (4x100 mL). The combined ether extracts are washed with brine, dried (MgSO4), and the azine product recrystallized. To form the thiadiazolidine, hydrogen sulfide is bubbled through a solution of the above azine (41.1 mmol), and 5 mg of p-toluenesilfonic acid in 300 mL of 1:3 acetone:benzene at ambient temperature. Conversion is complete after about 12 hours. The solvent is evaporated to give >90% of the thiadiazolidine. This material is used in the subsequent step without further purification. To prepare the thiadiazine,, a suspension of CaCO (20.7 g, 0.21 mol) in 300 mL of benzene at 0°C is added in several portions lead tetraacetate (20.7 g, 46.7 mmol). The mixture is stirred for about 20 min. A mixture of the above thiadiazolidine (35.9 mmol) and 300 mL of benzene is added dropwise with stirring over a period of about 1.5 hours. After the addition is complete, the mixture is stirred at ambient temperature for about 8 hours. Upon addition of 400 mL of water, a brown precipitate forms which is removed by filtration. The aqueous layer is separated, saturated with NaCl, and extracted with ether. The organic portions are combined, washed with brine, dried over MgSO4, and concentrated to give the thiadiazine with yields of about 90% as a yellow residue. This material is used in the subsequent step without further purification. To couple heterodiamondoids, an intimate mixture of thiadiazine (3.32 mmol) and triphenylphosphine (2.04 g, 7.79 mmol) is heated at 125-130 °C for about 12 hours under an atmosphere of nitrogen. Column chromatography of the residue over silica gel with suitable solvent gave about 70%) yield of the desired coupling products. All of the publications, patents and patent applications cited in this application are herein incorporated by reference in their entirety to the same extent as if the disclosure of each individual publication, patent application or patent was specifically and individually indicated to be incorporated by reference in its entirety. Many modifications of the exemplary embodiments of the invention disclosed above will readily occur to those skilled in the art. Accordingly, the invention is to be construed as including all structure and methods that fall within the scope of the appended claims.

Claims

WHAT IS CLAIMED IS:
1. A field emission device having a cathode, wherein the cathode comprises a heterodiamondoid.
2. The field emission device of claim 1, wherein the heterodiamondoid is part of a heterodiamondoid-containing material.
3. The field emission device of claim 1, wherein the heterodiamondoid comprises a derivatized heterodiamondoid.
4. The field emission device of claim 1, wherein the heterodiamondoid comprises an underivatized heterodiamondoid.
5. The field emission device of claim 1, wherein the heterodiamondoid comprises a heteroatom-containing lower diamondoid.
6. The field emission device of claim 1, wherein the heterodiamondoid comprises a heteroatom-containing higher diamondoid.
7. The field emission device of claim 6, wherein the heteroatom-containing higher diamondoid is synthesized from a diamondoid selected from the group consisting of tetramantane, pentamantane, hexamantane, heptamantane, octamantane, nonamantane, decamantane, and undecamantane.
8. The field emission device of claim 2, wherein the heterodiamondoid- containing material is a film.
9. The field emission device of claim 2, wherein the heterodiamondoid- containing material is a fiber.
10. The field emission device of claim 2, wherein the heterodiamondoid- containing material is selected from the group consisting of a heterodiamondoid- containing polymer, a heterodiamondoid-containing CND film, and a heterodiamondoid-containing molecular crystal.
11. The field emission device of claim 10, wherein the heterodiamondoid content of the cathode ranges from about 1 to 100 percent by weight for the heterodiamondoid-containing polymer.
12. The field emission device of claim 10, wherein the heterodiamondoid content of the cathode ranges from about 1 to 100 percent by weight for the heterodiamondoid-containing CND film.
13. The field emission device of claim 10, wherein the heterodiamondoid content of the cathode ranges from about 1 to 100 percent by weight for the heterodiamondoid-containing molecular crystal.
14. The field emission device of claim 11, wherein the electron affinity of the cathode is negative.
15. The field emission device of claim 12, wherein the electron affinity of the cathode is negative.
16. The field emission device of claim 13, wherein the electron affinity of the cathode is negative.
17. The field emission device of claim 11, wherein the electron affinity of the cathode is less than about 3.0 eN.
18. The field emission device of claim 12, wherein the electron affinity of the cathode is less than about 3.0 eN.
19. The field emission device of claim 13, wherein the electron affinity of the cathode is less than about 3.0 eN.
20. The field emission device of claim 2, further including an anode positioned adjacent to the cathode, and a power supply for supplying a potential difference between the anode and the cathode.
21. The field emission device of any of claim 20, where the potential difference that is applied between the anode and the cathode is less than about 10 volts.
22. The field emission device of any of claim 2, wherein the surface of the heterodiamondoid-containing material comprises carbon atoms that are substantially sp -hybridized.
23. The field emission device of any of claim 3 , wherein the surface of the heterodiamondoid-containing material is derivatized such that the surface comprises both sp2 and sp3 -hybridized carbon.
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WO2005076825A2 (en) 2005-08-25
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WO2005076825A3 (en) 2007-02-15
US7312562B2 (en) 2007-12-25
KR20070012338A (en) 2007-01-25
JP2007524974A (en) 2007-08-30

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